阅读说明：本技术 印刷用原版、印刷用原版层叠体、印刷版的制版方法及印刷方法 (Original printing plate, laminate of original printing plates, method for making printing plate, and printing method ) 是由 岛中修知 渡边骏平 于 2019-09-26 设计创作，主要内容包括：本发明提供一种印刷用原版、印刷用原版层叠体、印刷版的制版方法及印刷方法,上述印刷用原版在铝支承体的印刷面侧具有包含粒子的层,上述粒子的弹性模量为0.1GPa以上,在将上述印刷面侧的最外层表面的Bekk平滑度设为a秒的情况下,满足特定的式(1)。(The invention provides a printing original plate, a printing original plate laminate, a plate making method of a printing plate and a printing method, wherein the printing original plate comprises a layer containing particles on the printing surface side of an aluminum support, the elastic modulus of the particles is more than 0.1GPa, and the Bekk smoothness of the outermost surface on the printing surface side is a seconds, so that the specific formula (1) is satisfied.)

1. A printing original plate, wherein,

the aluminum support has a layer containing particles on the printing surface side, the particles have an elastic modulus of 0.1GPa or more, and satisfy the following formula (1) when the Bekk smoothness of the outermost surface on the printing surface side is defined as a seconds,

a≤1000 (1)。

2. a printing master according to claim 1,

bekk smoothness a second of the outermost surface on the printing surface side satisfies the following formula (2),

a≤300 (2)。

3. A printing original plate according to claim 1 or 2,

wherein the Bekk smoothness of the outermost surface on the printing surface side is defined as a seconds, and the Bekk smoothness of the outermost surface on the side opposite to the printing surface side is defined as b seconds, the following formulas (1) and (3) are satisfied,

a≤1000 (1)

1/a+1/b≥0.002 (3)。

4. a printing master according to any of claims 1 to 3,

the arithmetic average height Sa of the outermost surface on the printing surface side is 0.3 to 20 [ mu ] m.

5. A printing master according to any of claims 1 to 4,

the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface is 0.1 to 20 [ mu ] m.

6. A printing master according to any of claims 1 to 5,

the sum of the arithmetic average height Sa of the outermost surface on the printing surface side and the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface side exceeds 0.3 μm and is 20 μm or less.

7. A printing master according to any of claims 1 to 6,

the elastic modulus of the particles is 0.7GPa or more.

8. A printing master according to any of claims 1 to 7,

The printing surface side has an image recording layer.

9. A printing master according to claim 8,

the image recording layer contains an infrared absorber, a polymerization initiator, a polymerizable compound, and a polymer compound.

10. A printing master according to claim 9, wherein,

the polymer compound is a polymer compound containing styrene and/or acrylonitrile as a constituent unit.

11. A printing original plate according to claim 9 or 10, comprising two or more of the polymerizable compounds.

12. A printing original plate according to any one of claims 8 to 11,

the image recording layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 [ mu ] m, and the particles have an in-plane density of 10000 particles/mm²The following.

13. A printing master according to any of claims 8 to 12,

the printing surface side has a protective layer.

14. A printing master according to claim 13, wherein,

the protective layer comprises a water-soluble polymer.

15. A printing master according to claim 14, wherein,

the water-soluble polymer is polyvinyl alcohol having a saponification degree of 50% or more.

16. A printing master according to any of claims 13 to 15,

the protective layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 [ mu ] m, and the particles have an in-plane density of 10000 particles/mm²The following.

17. A printing master according to any of claims 13 to 16,

the thickness of the protective layer is less than 0.2 μm.

18. A printing master according to any of claims 1 to 7,

the printing surface side has a non-photosensitive resin layer.

19. A printing master according to claim 18,

the non-photosensitive resin layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 [ mu ] m, and the particles have an in-plane density of 10000 particles/mm²The following.

20. A printing master according to claim 18 or 19,

the printing surface side has a protective layer.

21. A printing master according to claim 20, wherein,

the protective layer comprises a water-soluble polymer.

22. A printing master according to claim 21, wherein,

the water-soluble polymer is polyvinyl alcohol having a saponification degree of 50% or more.

23. A printing master according to any of claims 20 to 22,

the protective layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 [ mu ] m, and the particles have an in-plane density of 10000 particles/mm²The following.

24. A printing master according to any of claims 20 to 23,

the thickness of the protective layer is less than 0.2 μm.

25. A printing original plate laminate obtained by laminating a plurality of printing original plates according to any one of claims 1 to 24, wherein the outermost layer on the printing surface side and the outermost layer on the side opposite to the printing surface side are laminated in direct contact with each other.

26. A method of making a printing plate, comprising: a step of image-exposing the printing original plate according to any one of claims 8 to 17; and a step of producing a printing plate by supplying at least one of a printing ink and a dampening solution and removing the unexposed portion of the image recording layer on the printing machine.

27. A method of making a printing plate, comprising: a step of image-exposing the printing original plate according to any one of claims 8 to 17; and a step of supplying a developing solution having a pH of 2 to 12 to remove the unexposed portion of the image recording layer to produce a printing plate.

28. A method of making a printing plate, comprising: a step of image-exposing the printing original plate according to any one of claims 8 to 17; and a step of removing the unexposed portion of the image recording layer by supplying a developing solution having a pH of 2 or more and 10 or less, wherein the step of removing the unexposed portion does not include a water washing step.

29. A method of printing, comprising: a step of image-exposing the printing original plate according to any one of claims 8 to 17; a step of producing a printing plate by supplying at least one of a printing ink and a dampening solution and removing an unexposed portion of the image recording layer on a printing machine; and a step of printing with the obtained printing plate.

30. A method of printing, comprising: a step of image-exposing the printing original plate according to any one of claims 8 to 17; a step of supplying a developing solution having a pH of 2 to 12 to remove an unexposed portion of the image recording layer to produce a printing plate; and a step of printing by using the obtained printing plate.

31. A method of printing, comprising: a step of image-exposing the printing original plate according to any one of claims 8 to 17; a plate making step of removing an unexposed portion of the image recording layer by supplying a developer having a pH of 2 or more and 10 or less, and not including a water washing step after the unexposed portion removing step; and a step of printing by using the obtained printing plate.

32. A plate making method of a printing plate, comprising the steps of: producing a printing plate by supplying at least one of a printing ink and a fountain solution without image-exposing the printing original plate according to any one of claims 18 to 24 and removing the non-photosensitive resin layer on a printing press.

33. A plate making method of a printing plate, comprising the steps of: a printing plate is produced by supplying a developer having a pH of 2 or more and 12 or less and removing the non-photosensitive resin layer without image-exposing the printing original plate according to any one of claims 18 to 24.

34. A printing method comprising the steps of: preparing a printing plate by supplying at least one of a printing ink and a fountain solution without image-exposing the original printing plate according to any one of claims 18 to 24 and removing the non-photosensitive resin layer on a printing press; and printing with the obtained printing plate.

35. A printing method comprising the steps of: preparing a printing plate by supplying a developer having a pH of 2 or more and 12 or less without image-exposing the original printing plate according to any one of claims 18 to 24 and removing the non-photosensitive resin layer; and printing with the obtained printing plate.

Technical Field

The present invention relates to a printing original plate, a printing original plate laminate, a plate making method for a printing plate, and a printing method.

Background

A printing original plate, for example, a lithographic printing plate original plate is often stored and transported as a laminate in which a plurality of printing plates are stacked. In this laminated body, interleaving paper is usually inserted between the planographic printing plate precursor plates for the purpose of preventing displacement of the planographic printing plate precursor plates, preventing adhesion between the planographic printing plate precursor plates, and preventing scratches on the image-recording layer side surfaces of the planographic printing plate precursor plates. However, the use of the interleaf paper itself involves problems such as cost increase and disposal, and also requires removal before the exposure step, and therefore, there is a risk that a load is applied to the plate making step and a defect in the peeling of the interleaf paper occurs. In addition, when removing the interleaf paper, it is necessary to consider that the surface of the lithographic printing plate precursor on the image-recording layer side is not damaged. Therefore, it is necessary to develop a lithographic printing plate precursor that can be laminated without interleaving paper.

As a lithographic printing plate precursor that can be laminated without interleaving paper, patent document 1 describes a negative-working lithographic printing plate precursor having, in the uppermost layer, a protective layer containing organic resin fine particles surface-coated with a hydrophilic polymer and silica, and a laminate obtained by laminating the same. Patent document 2 describes a requirement capable of forming an image, in which an image-formable layer contains about 0.01 to 10 wt% of silicate-coated polymer particles having a diameter of about 1 to about 20 μm, depending on the weight of an image-formable composition and an image-formable layer, and a laminate obtained by laminating the requirements capable of forming an image, and the requirement capable of forming an image contains a photothermal conversion material.

Prior art documents

Patent document

Patent document 1: japanese laid-open patent publication No. 2008-015503

Patent document 2: japanese Kokai publication No. 2006-516758

Disclosure of Invention

Technical problem to be solved by the invention

Lithographic printing plate precursors (hereinafter, also referred to as "precursors") are generally laminated with interleaving paper interposed therebetween for the following purposes: preventing plate integration displacement when manufacturing an original plate; preventing sticking of the master plates to each other; preventing multiple plate feeding in a plate making process of taking out original plates from an integrated body one by one; scratch and the like are prevented in a series of steps such as original plate manufacturing, integration, transportation, user plate making, and before printing. However, there is a case where no interleaving paper is included (also referred to as "interleaving paper reduction") in order to prevent a failure of interleaving paper peeling during plate making by a user, to improve plate making speed, and to reduce cost.

In the case of reducing the mount, as described above, a method of containing resin particles in the surface layer (outermost layer) may be used. However, when the outermost layer contains resin particles and projections are provided on the surface of the outermost layer, a new problem arises. For example, the projection may come off during the production, integration, and transportation of the original plate, scratches may be generated by the projection, and development delay may be generated by the projection.

That is, the lithographic printing plate precursor is required to have excellent properties such as plate feed prevention performance for a plurality of times in the process of taking out the precursor from the integrated body, falling prevention performance of the convex portions provided to the outermost surface of the precursor, scratch prevention performance due to the convex portions provided to the outermost surface of the precursor, and development delay prevention performance due to the convex portions provided to the outermost surface of the precursor. However, the techniques described in patent documents 1 and 2 have poor development delay prevention properties, and cannot satisfy all of the above characteristics.

The present invention addresses the problem of providing a printing original plate having excellent properties such as prevention of multiple feeding of a plate, prevention of falling off of projections provided on the outermost surface of the original plate, prevention of scratching caused by projections provided on the outermost surface of the original plate, and prevention of development delay caused by projections provided on the outermost surface of the original plate, even in a step of removing the original plate from an integrated body, and a printing original plate laminate using the printing original plate, a method for producing a printing plate, and a printing method.

Means for solving the technical problem

The means for solving the above problems include the following means.

＜1＞

A printing original plate, wherein,

the aluminum support has a layer containing particles on the printing surface side, the particles have an elastic modulus of 0.1GPa or more, and the Bekk smoothness of the outermost surface on the printing surface side is defined as a seconds, and the following formula (1) is satisfied.

a≤1,000 (1)

＜2＞

A printing original plate according to < 1 >, wherein,

the Bekk smoothness a second of the outermost surface on the printing surface side satisfies the following formula (2).

a≤300 (2)

＜3＞

The original printing plate according to < 1 > or < 2 >, wherein,

when the Bekk smoothness of the outermost surface on the printing surface side is defined as a seconds, and the Bekk smoothness of the outermost surface on the side opposite to the printing surface side is defined as b seconds, the following formulas (1) and (3) are satisfied.

a≤1,000 (1)

1/a+1/b≥0.002 (3)

＜4＞

The original printing plate according to any of < 1 > to < 3 >, wherein,

the arithmetic average height Sa of the outermost surface on the printing surface side is 0.3 to 20 μm.

＜5＞

The original printing plate according to any of < 1 > to < 4 >, wherein,

the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface is 0.1 to 20 μm.

＜6＞

The original printing plate according to any of < 1 > to < 5 >, wherein,

the sum of the arithmetic average height Sa of the outermost surface on the printing surface side and the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface side exceeds 0.3 μm and is 20 μm or less.

＜7＞

The original printing plate according to any of < 1 > to < 6 >, wherein,

the elastic modulus of the particles is 0.7GPa or more.

＜8＞

The original printing plate according to any of < 1 > to < 7 >, wherein,

the printing surface side has an image recording layer.

＜9＞

An original plate for printing according to < 8 >, wherein,

the image recording layer contains an infrared absorber, a polymerization initiator, a polymerizable compound, and a polymer compound.

＜10＞

The original printing plate according to < 9 >, wherein,

the polymer compound is a polymer compound containing styrene and/or acrylonitrile as a constituent unit.

＜11＞

A printing original plate according to < 9 > or < 10 > comprising two or more of the above-mentioned polymerizable compounds.

＜12＞

The original printing plate according to any of < 8 > to < 11 >, wherein,

the image recording layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 μm, and the particles have an in-plane density of 10,000 particles/mm ²The following.

＜13＞

The original printing plate according to any of < 8 > to < 12 >, wherein,

the printing surface side has a protective layer.

＜14＞

An original plate for printing according to < 13 >, wherein,

the protective layer includes a water-soluble polymer.

＜15＞

A printing original plate according to < 14 >, wherein,

the water-soluble polymer is polyvinyl alcohol having a saponification degree of 50% or more.

＜16＞

The original printing plate according to any of < 13 > to < 15 >, wherein,

the protective layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 [ mu ] m, and the particles have an in-plane density of 10,000 particles/mm²The following.

＜17＞

The original printing plate according to any of < 13 > to < 16 >, wherein,

the thickness of the protective layer is less than 0.2 μm.

＜18＞

The original printing plate according to any of < 1 > to < 7 >, wherein,

the printing surface side has a non-photosensitive resin layer.

＜19＞

A printing original plate according to < 18 >, wherein,

the non-photosensitive resin layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 [ mu ] m, and the particles have an in-plane density of 10,000 pieces/mm²The following.

＜20＞

An original plate for printing according to < 18 > or < 19 >, wherein,

the printing surface side has a protective layer.

＜21＞

The original printing plate according to < 20 >, wherein,

the protective layer includes a water-soluble polymer.

＜22＞

An original plate for printing according to < 21 > wherein,

the water-soluble polymer is polyvinyl alcohol having a saponification degree of 50% or more.

＜23＞

A printing original plate according to any of < 20 > to < 22 >, wherein,

the protective layer is a layer containing the particles, the particles have an average particle diameter of 0.5 to 20 [ mu ] m, and the particles have an in-plane density of 10,000 particles/mm²The following.

＜24＞

The original printing plate according to any of < 20 > to < 23 >, wherein,

the thickness of the protective layer is less than 0.2 μm.

＜25＞

A laminated original printing plate, which is obtained by laminating a plurality of original printing plates of < 1 > to < 24 > and is laminated by directly contacting an outermost layer on the printing surface side and an outermost layer on the side opposite to the printing surface side.

＜26＞

A method of making a printing plate, comprising: a step of exposing the image of the original printing plate of any one of < 8 > to < 17 >; and a step of producing a printing plate by supplying at least one of a printing ink and a dampening solution and removing the unexposed portion of the image recording layer on the printing machine.

＜27＞

A method of making a printing plate, comprising: a step of exposing the image of the original printing plate of any one of < 8 > to < 17 >; and a step of supplying a developing solution having a pH of 2 to 12 to remove the unexposed portion of the image recording layer to produce a printing plate.

＜28＞

A method of making a printing plate, comprising: a step of exposing the image of the original printing plate of any one of < 8 > to < 17 >; and a step of removing the unexposed portion of the image recording layer by supplying a developing solution having a pH of 2 or more and 10 or less, wherein the step of removing the unexposed portion does not include a water washing step.

＜29＞

A method of printing, comprising: a step of exposing the image of the original printing plate of any one of < 8 > to < 17 >; a step of producing a printing plate by supplying at least one of a printing ink and a dampening solution and removing an unexposed portion of the image recording layer on a printing machine; and a step of printing with the obtained printing plate.

＜30＞

A method of printing, comprising: a step of exposing the image of the original printing plate of any one of < 8 > to < 17 >; a step of supplying a developing solution having a pH of 2 to 12 to remove an unexposed portion of the image recording layer to produce a printing plate; and a step of printing by using the obtained printing plate.

＜31＞

A method of printing, comprising: a step of exposing the image of the original printing plate of any one of < 8 > to < 17 >; a plate making step of removing an unexposed portion of the image recording layer by supplying a developer having a pH of 2 or more and 10 or less, and not including a water washing step after the unexposed portion removing step; and a step of printing by using the obtained printing plate.

＜32＞

A plate making method of a printing plate, comprising the steps of: the printing plate is produced by supplying at least one of a printing ink and a fountain solution to the printing plate without image-exposing the printing plate precursor of any of < 18 > to < 24 > and removing the non-photosensitive resin layer on a printing machine.

＜33＞

A plate making method of a printing plate, comprising the steps of: the printing plate is produced by supplying a developing solution having a pH of 2 to 12 without image-exposing the printing original plate of < 18 > to < 24 > and removing the non-photosensitive resin layer.

＜34＞

A printing method comprising the steps of: preparing a printing plate by supplying at least one of a printing ink and a fountain solution to the printing plate without image-exposing the original printing plate of < 18 > to < 24 > and removing the non-photosensitive resin layer on a printing machine; and printing with the obtained printing plate.

＜35＞

A printing method comprising the steps of: preparing a printing plate by supplying a developing solution having a pH of 2 or more and 12 or less without image-exposing the printing original plate of < 18 > to < 24 > and removing the non-photosensitive resin layer; and printing with the obtained printing plate.

Effects of the invention

According to the present invention, it is possible to provide a printing original plate excellent in characteristics such as prevention of plate feeding, prevention of falling off of convex portions provided to the outermost surface of the original plate, prevention of scratches caused by the convex portions provided to the outermost surface of the original plate, and prevention of development delay caused by the convex portions provided to the outermost surface of the original plate, even when the number of times of plate feeding in the step of taking out the original plate from the integrated body is reduced, a printing original plate laminate using the printing original plate, a plate making method for a printing plate, and a printing method.

Drawings

FIG. 1 is a graph showing an example of an alternate waveform current waveform pattern used in an electrochemical roughening treatment.

Fig. 2 is a side view showing an example of radial cells in the electrochemical roughening treatment using alternating current.

Fig. 3 is a schematic view of an anodizing apparatus used in the anodizing process.

Fig. 4 is a schematic diagram showing a configuration of an example of a developing apparatus which can be preferably used in the present invention.

Fig. 5 is a side view showing a concept of a brushing step used in a mechanical roughening treatment in the production of an aluminum support.

Detailed Description

The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, "to" indicating a numerical range is used in a meaning including numerical values described before and after the range as a lower limit value and an upper limit value.

In the labeling of the group (atomic group) in the present specification, the label not labeled with substitution and unsubstituted includes not only a group having no substituent but also a group having a substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "(meth) acrylic acid" is a term used as a term including both acrylic acid and methacrylic acid, and "(meth) acryloyl group" is a term used as a term including both acryloyl group and methacryloyl group.

The term "step" in the present specification includes not only an independent step but also a step that can achieve the intended purpose of the step even when the step cannot be clearly distinguished from other steps.

In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.

Unless otherwise specified, the mass average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights obtained by Gel Permeation Chromatography (GPC) analysis using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (each trade name manufactured by TOSOH CORPORATION), detection using a solvent THF (tetrahydrofuran), and a differential refractometer, and conversion into polystyrene as a standard substance.

In the present specification, the term "original printing plate" includes not only lithographic printing plate precursors but also waste printing plate precursors for printing. The term "printing plate" includes not only a lithographic printing plate produced by exposing and developing a printing original plate as needed, but also a waste printing plate for printing. In the case of a waste plate precursor for printing, the operations of exposure and development are not necessarily required. The waste printing plate is a printing plate to be mounted on an unused plate cylinder when printing a part of a printing surface in monochrome or two-color in color press printing, for example. The waste printing plate is also referred to as a water plate, a dummy plate, a blank plate, or the like.

The present invention will be described in detail below.

[ original edition for printing ]

The original printing plate according to the present invention has a layer containing particles on the printing surface side of an aluminum support (hereinafter, also simply referred to as "support"), the particles having an elastic modulus of 0.1GPa or more, and satisfying the following formula (1) when the Bekk smoothness of the outermost surface on the printing surface side is defined as a seconds.

a≤1,000 (1)

As a result of intensive studies, the inventors of the present invention have found that, by adopting the above-described configuration, the original printing plate according to the present invention can provide an original printing plate having excellent properties such as the prevention of plate feeding a plurality of times in the step of removing the original printing plate from the integrated body, the prevention of falling off of the convex portions provided on the outermost surface of the original printing plate, the prevention of scratches caused by the convex portions provided on the outermost surface of the original printing plate, and the prevention of development delay caused by the convex portions provided on the outermost surface of the original printing plate.

Although the mechanism by which the above-described excellent effects can be obtained is not clear, it is presumed that the following is obtained. In the original printing plate according to the present invention, when the integrated body is formed of the convex portions of the outermost surface such that Bekk smoothness a seconds imparted to the outermost surface on the printing surface side satisfies formula (1), a gap into which air can flow is formed between the contacting original plates, and therefore, the effect of preventing plate feeding from being performed a plurality of times is expected. Further, since the contained particles have a high elastic modulus of 0.1GPa or more, the particles are less likely to be deformed by a pressure during lamination or the like, and the pressure-contact area of the image recording layer (or the non-photosensitive resin layer) can be reduced. Since the larger the pressure contact area is, the more difficult the development is, the original printing plate according to the present invention having a small pressure contact area is considered to have the effect of preventing the development delay.

The original printing plate according to the present invention has a layer containing particles having an elastic modulus of 0.1GPa or more on the printing surface side of an aluminum support (hereinafter also referred to as "support").

Here, the "printing surface side" of the aluminum support refers to a side to which printing ink is applied at the time of printing. The lithographic printing plate precursor has an image recording layer, and the waste printing plate precursor for printing has a non-photosensitive resin layer.

The "side opposite to the printing surface side" is a side (non-printing surface side) opposite to the printing surface side of the aluminum support, and refers to a side that comes into contact with a plate cylinder of the printing press at the time of printing.

The printing original plate according to the present invention may have an undercoat layer on the printing surface side on the support. The support may have a back coat layer on the side opposite to the printing surface side.

The printing original plate according to the present invention may be a printing original plate used for on-press development or a printing original plate used for development with a developer.

The original printing plate according to the present invention has a layer containing particles on the printing surface side of the support.

The particles contained in the layer containing particles (hereinafter also referred to as a particle-containing layer) are preferably at least one type of particles selected from organic resin particles and inorganic particles.

The organic resin particles are preferably particles composed of polyolefins such as poly (meth) acrylates, polystyrene and derivatives thereof, polyamides, polyimides, low-density polyethylene, high-density polyethylene, and polypropylene, synthetic resins such as polyurethane, polyurea, and polyesters, and particles composed of natural polymers such as chitin, chitosan, cellulose, crosslinked starch, and crosslinked cellulose.

Among them, synthetic resin particles have advantages such as easy control of particle size and easy control of desired surface properties by surface modification.

As for the method for producing the organic resin particles, for example, fine particles can be formed by a crushing method using a relatively hard resin such as polymethyl methacrylate (PMMA), but a method of synthesizing particles by an emulsion suspension polymerization method is preferably employed in view of easiness in control of particle size and accuracy.

The method for producing organic resin particles is described in detail in "ultrafine particles and materials" published by the society of Japan Material science, Shokobo 1993, "production and application of particles/powder" Chuanchun Mayau, CMC published 2005, and the like.

The organic resin particles can also be obtained as commercially available products, and examples thereof include Soken Chemical & Engineering Co., LTD. Cross-linked acrylic resins MX-40T, MX-80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-1000, MX-1500H, MR-2HG, MR-7HG, MR-10HG, MR-3GSN, MR-5GSN, MR-7G, MR-10G, MR-5C, MR-7GC, styrene resin systems SX-350H, SX-500H, Sekisui Plastics Co., Ltd. acrylic resin MBX-5, MBX-8, MBX-12, MBX-15, MBX-20, MB20X-5, MB30X-5, MB30X-8, MB30X-20, SBX-6, SBX-8, SBX-12, SBX-17, Mitsui Chemicals, inc, polyolefin resin, CHEMIPEARL W100, W200, W300, W308, W310, W400, W401, W405, W410, W500, WF640, W700, W800, W900, W950, WP100, and the like.

Examples of the inorganic particles include silica, alumina, zirconia, titania, carbon black, graphite, and BaSO₄、ZnS、MgCO₃、CaCO₃、ZnO、CaO、WS₂、MoS₂、MgO、SnO₂、α-Fe₂O₃、α-FeOOH、SiC、CeO₂BN, SiN, MoC, BC, WC, titanium carbide, corundum, synthetic diamond, garnet, silica, Triboli, diatomaceous earth, dolomite, and the like.

The particles are preferably particles having a hydrophilic surface. The particles having a hydrophilic surface include organic resin particles having a hydrophilic surface and inorganic particles having a hydrophilic surface.

The organic resin particles having a hydrophilic surface are preferably organic resin particles coated with at least one inorganic compound selected from the group consisting of silica, alumina, titania and zirconia, and particularly preferably organic resin particles coated with silica.

The organic resin constituting the organic resin particles having a hydrophilic surface is preferably at least one resin selected from the group consisting of polyacrylic resins, polystyrene resins, polyester resins, epoxy resins, phenolic resins, and melamine resins.

Hereinafter, the organic resin particles having a hydrophilic surface will be described in detail by taking the organic resin particles coated with silica (hereinafter, also referred to as "silica-coated organic resin particles") as an example, but the organic resin particles having a hydrophilic surface in the present invention are not limited thereto.

The silica-coated organic resin particles are particles in which particles composed of an organic resin are surface-coated with silica. The organic resin particles constituting the core are preferably not softened or sticky by moisture or temperature in the air.

Examples of the organic resin constituting the organic resin particles in the silica-coated organic resin particles include polyacrylic resins, polystyrene resins, polyester resins, epoxy resins, phenol resins, melamine resins, and the like.

The material for forming the silica layer coating the surface of the silica-coated organic resin particle preferably includes a compound having an alkoxysilyl group such as a condensate of an alkoxysiloxane-based compound, and particularly preferably includes a siloxane-based material, and specifically, preferably includes silica particles such as a silica sol, colloidal silica, and silica nanoparticles.

The structure of the silica-coated organic resin particles may be a structure in which silica particles are adhered as a solid component on the surface of the organic resin particles, or a structure in which a siloxane compound layer is formed on the surface of the organic resin particles by condensation reaction of an alkoxysiloxane compound.

The silica does not necessarily have to coat the entire region of the surface of the organic resin particle, and the surface is preferably coated in an amount of 0.5 mass% or more with respect to at least the total mass of the organic resin particles. That is, the presence of silica in at least a part of the surface of the organic resin particle makes it possible to improve the affinity of the water-soluble polymer coexisting in the surface of the organic resin particle, for example, to polyvinyl alcohol (PVA), and to suppress the falling off of the particle even when an external stress is applied, and to maintain excellent scratch resistance and ease of peeling when the particles are laminated without using a backing paper. Therefore, "coated with silica" in the present invention also includes a state where silica is present in at least a part of the surface of the organic resin particle as such.

The surface coating state of the silica can be confirmed by morphological observation with a Scanning Electron Microscope (SEM) or the like. The amount of silica coating can be confirmed by detecting Si atoms by elemental analysis such as fluorescent X-ray analysis and calculating the amount of silica present in the Si atoms.

The method for producing the organic resin particles coated with silica is not particularly limited, and may be a method of forming the silica surface coating layer while forming the organic resin particles by allowing the silica particles or the silica precursor compound to coexist with monomer components which become raw materials of the organic resin particles, or a method of forming the organic resin particles, then physically adhering the silica particles to the surface, and then immobilizing the same.

The following is 1 example of a method for producing silica-coated organic resin particles. First, silica and a raw resin (more specifically, a raw resin such as a suspension-polymerizable monomer, a suspension-crosslinkable prepolymer, or a resin solution constituting the organic resin) are added to water containing a suspension stabilizer appropriately selected from a water-soluble polymer such as polyvinyl alcohol, methylcellulose, or polyacrylic acid, or an inorganic suspension agent such as calcium phosphate or calcium carbonate, and stirred and mixed to prepare a suspension in which silica and the raw resin are dispersed. In this case, a suspension having a desired particle diameter can be formed by adjusting the type of the suspension stabilizer, the concentration thereof, the number of times of stirring, and the like. Then, the suspension is heated to initiate a reaction, and the resin raw material is suspension-polymerized or suspension-crosslinked to produce resin particles. In this case, the coexisting silica is fixed to the resin particles cured by polymerization or crosslinking reaction, and is fixed in the vicinity of the surface of the resin particles particularly due to the physical properties thereof. Then, the suspension is subjected to solid-liquid separation, and the suspension stabilizer adhering to the particles is removed by washing and dried. In this way, approximately spherical silica-coated organic resin particles having a desired particle diameter and obtained by fixing silica can be obtained.

In this way, the conditions can be controlled at the time of suspension polymerization or suspension crosslinking to obtain silica-coated organic resin particles having a desired particle diameter, and silica-coated organic resin particles having a desired size can be obtained by a mesh filtration method or the like after the silica-coated organic resin particles are produced without strictly performing such control.

The amount of the raw material added to the mixture when the silica-coated organic particles are produced by the above method is preferably, for example, as follows: when the total amount of the raw material resin and the silica is 100 parts by mass, first, 0.1 to 20 parts by mass of a suspension stabilizer is added to 200 to 800 parts by mass of water as a dispersion medium and sufficiently dissolved or dispersed, the mixture of the raw material resin and the silica is added to the liquid in 100 parts by mass, the mixture is stirred while adjusting the stirring speed so that the dispersed particles have a predetermined particle size, and after the particle size adjustment, the liquid temperature is raised to 30 to 90 ℃ and the reaction is carried out for 1 to 8 hours.

Regarding the method for producing the silica-coated organic resin particles, the above-mentioned method is 1 example thereof, and for example, silica-coated organic resin particles obtained by the methods described in detail in japanese patent laid-open nos. 2002-327036, 2002-173410, 2004-307837, 2006-038246, and the like can also be preferably used in the present invention.

Further, the organic resin particles coated with silica can be also obtained as a commercially available product, and specific examples thereof include those made by Negami Chemical Industrial Co., Ltd, ART PEARL G-200 transparency, ART PEARL G-400 transparency, ART PEARL G-800 transparency, ART PEARL GR-400 transparency, ART PEARL GR-600 transparency, ART PEARL GR-800 transparency, and ART PEARL J-7P.

The organic resin particles used in the present invention have been described above by taking the organic resin particles coated with silica as an example, but the organic resin particles coated with aluminum dioxide, titanium dioxide, or zirconium dioxide can also be carried out in the same manner by using aluminum dioxide, titanium dioxide, or zirconium dioxide instead of silica.

The shape of the particles is preferably a spherical shape, but may be a flat plate shape or a so-called spindle shape which is elliptical in a projection view.

The particles contained in the particle-containing layer are not particularly limited as long as they have an elastic modulus of 0.1GPa or more.

From the viewpoint of development delay prevention, it is desirable that the elastic modulus of the particles contained in the particle-containing layer is high. The elastic modulus is preferably 0.7GPa or more, and more preferably 1.25GPa or more.

Regarding the elastic modulus of the particles contained in the particle-containing layer, a micro hardness tester (PICODE NTOR HM500, manufactured by fish INSTRUMENTS k.k.) was used to load: a plane indenter (50 mm. times.50 mm) was pressed at 1mN/2sec for measurement, and the load-displacement curve obtained was fitted to the following contact type (Hertz type) of a plate and a ball and calculated.

[ numerical formula 1]

E₁Modulus of elasticity of ball

δ: displacement amount

R₀Radius of particle

v₁Poisson ratio of ball

P is the load

As the particles having an elastic modulus of 0.1GPa or more, there may be mentioned, in addition to the ART PEARL G-200 transparency, ART PEARL G-400 transparency, ART PEARL G-800 transparency, ART PEARL GR-400 transparency, ART PEARL GR-600 transparency, ART PEARL GR-800 transparency and ART PEARL J-7P, ART PEARL J-4P, ART PEARL J-5P, ART PEARL J-6P, ART PEARL J-3PY, ART PEARL J-4PY, ART PEARL J-6PF, ART PEARL J-7PY (hereinafter referred to as Negami chemical Industrial Co., Ltd.), PEARL 120, TOSPEARL 130, TOSPEARL 145 and TOSPEARL 2000B (hereinafter referred to as motion Material working), etc.

The average particle diameter of the particles contained in the particle-containing layer is preferably 0.5 to 20 μm. The average particle diameter is more preferably 0.5 to 10 μm, and still more preferably 0.5 to 7 μm.

The average particle diameter of the particles contained in the particle-containing layer is a volume average particle diameter, and the volume average particle diameter is measured by a laser diffraction/scattering particle size distribution meter. Specifically, the measurement is carried out using a particle size distribution measuring apparatus "micro-trac MT-3300 II" (Nikkiso Co., LTD).

In the present invention, unless otherwise specified, the average particle diameter of other particles is also measured by the above-described measurement method.

The in-plane density of the particles in the particle-containing layer is preferably 10,000 particles/mm²The following. The in-plane density is more preferably 100 to 5000 pieces/mm²More preferably 100 to 3000 pieces/mm²。

The in-plane density of the particles in the particle-containing layer can be determined by observing the surface of the printing original plate with a Scanning Electron Microscope (SEM). Specifically, the in-plane density can be calculated by observing the surface of the original printing plate at position 5 with a scanning electron microscope (SE M), counting the number of particles, converting the number of particles into the number of particles per square millimeter of observation field area, and obtaining the average value of the numbers.

In the original printing plate according to the present invention, the Bekk smoothness of the outermost surface on the printing surface side satisfies the following formula (1) for a seconds.

a≤1,000 (1)

The Bekk smoothness a seconds of the outermost surface on the printing surface side preferably satisfies the following formula (2).

a≤300 (2)

The Bekk smoothness a second of the outermost surface on the printing surface side more preferably satisfies the following formula (2 a).

a≤100(2a)

The Bekk smoothness (Bekk seconds) of the outermost surface can be measured in accordance with JIS P8119 (1998). Specifically, the measurement was performed using KUMAGAI RIKI KOGYO co., ltd. a nike smoothness tester at 1/10 which is a standard air volume, that is, at an air volume of 1 mL.

In the original printing plate according to the present invention, the Bekk smoothness of the outermost surface on the printing surface side is defined as a seconds, and the Bekk smoothness of the outermost surface on the side opposite to the printing surface side is defined as b seconds, the following expressions (1) and (3) are satisfied.

a≤1,000 (1)

1/a+1/b≥0.002 (3)

When the Bekk smoothness a seconds and the Bekk smoothness b seconds satisfy the expressions (1) and (3), the effect of preventing multiple plate feeding is further improved.

The Bekk smoothness b seconds of the outermost surface on the side opposite to the printing surface side is preferably 1,000 seconds or less, more preferably 300 seconds or less, and further preferably 100 seconds or less.

The value of 1/a +1/b, which is the sum of the reciprocal of Bekk smoothness a seconds on the outermost surface on the printing surface side and the reciprocal of Bekk smoothness b seconds on the outermost surface on the opposite side from the printing surface side, is preferably 0.004 or more, and more preferably 0.01 or more.

a. b is preferably small, and the lower limit is not particularly limited, but preferably exceeds 0.

In the original printing plate according to the present invention, the mode for achieving Bekk smoothness a seconds of the outermost surface on the printing surface side satisfying the requirement of formula (1) is not particularly limited, but for example, a mode in which the outermost surface on the printing surface side has concavities and convexities as in the following modes a1, a2, and A3 is preferable.

< mode A1 >

Protective layerComprising particles having an average particle diameter of 0.5 to 20 μm and an in-plane density of 10,000 particles/mm²The following method is used.

< mode A2 >

The image recording layer contains particles having an average particle diameter of 0.5 to 20 μm and an in-plane density of 10,000 particles/mm²The following method is used.

< mode A3 >

The non-photosensitive resin layer contains particles having an average particle diameter of 0.5 to 20 μm and an in-plane density of 10,000 particles/mm²The following method is used.

In the original plate for printing according to the present invention, the arithmetic average height Sa of the outermost surface on the printing surface side is preferably 0.3 μm or more and 20 μm or less.

If the arithmetic average height Sa of the outermost surface on the printing surface side is 0.3 μm or more, a gap into which air can flow is formed between the contacting original plates when the integrated body is formed, and therefore the effect of preventing multiple plate feeding is improved. If the arithmetic average height Sa of the outermost surface on the printing surface side is 20 μm or less, the projection is suppressed to the depth of the image recording layer in the case of constituting an integrated body or the like, and the problem of development delay due to damage of the image recording layer does not occur. Further, when the arithmetic mean height Sa is 0.3 μm or more and 20 μm or less, the scratch preventive property is excellent.

The arithmetic average height Sa of the outermost surface on the printing surface side is more preferably 0.5 to 10 μm, and still more preferably 0.5 to 7 μm.

The arithmetic average height Sa of the outermost surface can be measured according to the method described in ISO 25178. Specifically, 3 or more samples were selected from the same samples and measured using a micromachine map MM3200-M100 manufactured by Ryoka Systems inc. The measurement range is set to be within a range of 1cm × 1cm randomly selected from the surface of the sample.

In the original plate for printing according to the present invention, the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface side is preferably 0.1 μm or more and 20 μm or less.

If the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface side is 0.1 μm or more and 20 μm or less, the convex portion of the outermost surface on the side opposite to the printing surface side is suppressed to the depth of the image recording layer in the case of constituting an integrated body or the like, and the problem of development delay due to damage of the image recording layer does not occur.

The outermost surface on the side opposite to the printing surface side includes a surface on the side opposite to the printing surface side of the support or a back coat surface.

The arithmetic average height Sa of the outermost surface on the side opposite to the printing surface side is more preferably 0.3 to 20 μm, still more preferably 0.5 to 10 μm, and particularly preferably 0.5 to 7 μm.

In the original plate for printing according to the present invention, the total value of the arithmetic average height Sa of the outermost surface on the printing surface side and the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface side exceeds 0.3 μm and is 20 μm or less.

When the total value of the arithmetic average height Sa of the outermost surface on the printing surface side and the arithmetic average height Sa of the outermost surface on the opposite side to the printing surface side exceeds 0.3 μm and is 20 μm or less, the effect of preventing multiple feeding and the effect of preventing development delay are improved.

The sum of the arithmetic average height Sa of the outermost surface on the side opposite to the printing surface and the arithmetic average height Sa of the outermost surface on the printing surface side is preferably 0.4 to 20 μm, more preferably 1 to 20 μm, and particularly preferably 1 to 14 μm.

The original plate for printing according to the present invention has an outermost layer (for example, a back coat layer) on the side opposite to the printing surface side of the support, and the Bekk smoothness b seconds of the outermost surface and the arithmetic average height Sa of the outermost surface can be adjusted to be within the above-described desired ranges by including the particles in the outermost layer or by forming projections on the outermost layer. Thus, the original printing plate according to the present invention is further excellent in the above properties.

< support >

The printing original plate according to the present invention has an aluminum support.

As the support used in the original printing plate according to the present invention, a known support can be used. Among them, an anodized aluminum plate is preferable, and a roughened and anodized aluminum plate is more preferable.

The roughening treatment and the anodizing treatment can be performed by a known method.

The aluminum plate can be appropriately selected and subjected to, as necessary, a pore enlargement treatment or a pore sealing treatment of the anodic oxide film described in japanese patent laid-open nos. 2001-253181 and 2001-322365, and a surface hydrophilization treatment based on an alkali metal silicate described in each specification of U.S. Pat. No. 2,714,066, 3,181,461, 3,280,734, and 3,902,734, or a polyvinylphosphonic acid described in each specification of U.S. Pat. No. 3,276,868, 4,153,461, and 4,689,272.

The center line average roughness Ra of the support is preferably 0.10 to 1.2 μm.

In the support, the average diameter of the micropores in the surface of the anodic oxide film is preferably 10 to 100 nm.

The aluminum support preferably has an aluminum plate and an anodic oxide film of aluminum disposed on the aluminum plate.

The aluminum plate (aluminum support) is a dimensionally stable metal having aluminum as a main component, and contains aluminum or an aluminum alloy. Examples of the aluminum plate include a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of a different element, and a plastic film or paper in which aluminum (alloy) is laminated or evaporated. Further, a composite sheet may be used in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese patent application laid-open No. 48-018327.

The aluminum alloy contains silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium, and the like as the different elements, and the content of the different elements in the alloy is 10 mass% or less with respect to the total mass of the alloy. The aluminum plate 18 is preferably a pure aluminum plate, but since it is difficult to produce pure aluminum from the viewpoint of smelting technology, a small amount of different elements may be contained.

The aluminum plate is not limited in composition, and known and commonly used materials (for example, JIS a 1050, JIS a 1100, JIS a 3103, and JIS a 3005) can be used as appropriate.

Preferably, the aluminum plate has a width of about 400mm to 2,000mm and a thickness of about 0.1mm to 0.6 mm. The width and thickness can be appropriately changed depending on the size of the printing press, the size of the printing plate, the target printed material to be obtained, and the like.

(anodic oxide coating)

The anodic oxide film is an anodic aluminum oxide film having micropores, which is produced on the surface of an aluminum plate by anodic oxidation treatment. The micropores extend in the thickness direction (aluminum plate side, depth direction) from the surface of the anodic oxide film on the side opposite to the aluminum plate.

The average diameter (average opening diameter) of the surface of the anodic oxide film of the micropores is preferably 7nm to 150nm, more preferably 10nm to 100nm, further preferably 10nm to 60nm, particularly preferably 15nm to 60nm, and most preferably 18nm to 40nm, from the viewpoint of color tone reproducibility, printing durability, and brush staining property.

The micropores in the anodic oxide film are preferably formed of large-diameter hole portions extending from the surface of the anodic oxide film to a position having a depth of 10nm to 1,000nm, and small-diameter hole portions communicating with the bottoms of the large-diameter hole portions and further extending from the communicating position to a position having a depth of 20 nm to 2,000 nm.

The large-diameter hole and the small-diameter hole will be described in detail below.

Large diameter hole section-

From the viewpoint of color tone reproducibility, printing durability, and brush staining, the average diameter (average opening diameter) of the anodic oxide film surface in the large-diameter hole portion is preferably 7nm to 150nm, more preferably 15nm to 150nm, even more preferably 15nm to 60nm, and particularly preferably 18nm to 40 nm.

The average diameter of the large-diameter hole portion was measured by a field emission type scanning electron microscope with a magnification of 15 ten thousand times(FE-SEM) the surface of the anodic oxide film was observed on 4 sheets of N, and the surface of the anodic oxide film was measured to be present at 400 × 600nm in 4 obtained images²The diameter (diameter) of the micropores (large-diameter hole portions) in the range of (a) and calculated as an arithmetic average of the diameters.

When the shape of the large-diameter hole is not circular, a circle-equivalent diameter is used. The "equivalent circle diameter" refers to a diameter of a circle when the shape of the opening is assumed to be a circle having a projection area equal to the projection area of the opening.

The bottom of the large-diameter hole is preferably located at a depth of 70nm to 1,000nm (hereinafter, also referred to as depth A) from the surface of the anodic oxide film. That is, the large-diameter pores are preferably pores extending from the surface of the anodic oxide film in the depth direction (thickness direction) by 70nm to 1,000 nm. Among them, the depth a is more preferably 90nm to 850nm, still more preferably 90nm to 800nm, and particularly preferably 90nm to 600nm, from the viewpoint of further improving the effects of the method for producing a lithographic printing plate precursor according to the present invention.

Further, a photograph (15 ten thousand times) of a cross section of the anodic oxide film was taken as the depth, and the depths of 25 or more large-diameter holes were measured and calculated as an arithmetic average value.

The shape of the large-diameter hole portion is not particularly limited, and examples thereof include a substantially straight tube shape (substantially cylindrical shape) and a conical shape having a diameter decreasing in the depth direction (thickness direction), and a substantially straight tube shape is preferable. The shape of the bottom of the large-diameter hole is not particularly limited, and may be a curved surface (convex) or a flat surface.

The inner diameter of the large-diameter hole is not particularly limited, but is preferably about the same size as the diameter of the opening or smaller than the diameter of the opening. The inner diameter of the large-diameter hole portion may be different from the diameter of the opening portion by about 1nm to 10 nm.

Small bore portion-

The small-diameter hole portion is a hole portion that communicates with the bottom of the large-diameter hole portion and extends further in the depth direction (thickness direction) from the communication position. One small-diameter hole is usually communicated with one large-diameter hole portion, but 2 or more small-diameter hole portions may be communicated with the bottom of one large-diameter hole portion.

The average diameter at the communication position of the small-diameter hole portion is preferably 13nm or less, more preferably 11nm or less, and particularly preferably 10nm or less. The lower limit is not particularly limited, but is preferably 5nm or more.

The average diameter of the small-diameter hole portion can be calculated as follows: the surface of the anodic oxide film 20 was observed with 4 FE-SEM at a magnification of 15 ten thousand times, and the surface of the anodic oxide film was measured to be present at 400 × 600nm in 4 images obtained ²The diameter (diameter) of the micropores (small-diameter hole portions) in the range of (1) and the arithmetic average of the diameters is obtained. When the depth of the large-diameter hole is deep, the upper portion of the anodic oxide film (the region having the large-diameter hole) may be cut (for example, by argon gas) as necessary, and then the surface of the anodic oxide film 20 may be observed by the FE-SEM to determine the average diameter of the small-diameter hole.

When the small-diameter hole portion is not circular, the equivalent circle diameter is used. The "equivalent circle diameter" refers to a diameter of a circle when the shape of the opening is assumed to be a circle having a projection area equal to the projection area of the opening.

The bottom of the small-diameter hole is preferably located at a position extending from a position (corresponding to the depth a) communicating with the large-diameter hole to 20nm to 2,000nm in the depth direction. In other words, the small-diameter pores are pores extending in the depth direction (thickness direction) from the positions communicating with the large-diameter pores, and the depth of the small-diameter pores is preferably 20nm to 2,000nm, more preferably 100nm to 1,500nm, and particularly preferably 200nm to 1,000 nm.

Further, a photograph (5 ten thousand times) of a cross section of the anodic oxide film was taken as the depth, and the depths of 25 or more small-diameter holes were measured and calculated as an arithmetic average value.

The shape of the small-diameter hole portion is not particularly limited, and examples thereof include a substantially straight tube shape (substantially cylindrical shape) and a conical shape whose diameter becomes smaller toward the depth direction, and a substantially straight tube shape is preferable. The shape of the bottom of the small-diameter hole is not particularly limited, and may be a curved surface (convex) or a planar surface.

The inner diameter of the small-diameter hole portion is not particularly limited, but may be about the same as the diameter at the communication position, or may be smaller than the diameter or larger than the diameter. The inner diameter of the small-diameter hole portion may be generally different from the diameter of the opening by about 1nm to 10 nm.

The ratio of the average diameter on the surface of the anodic oxide film in the large-diameter hole portion to the average diameter at the communication position of the small-diameter hole portion, (average diameter on the surface of the anodic oxide film in the large-diameter hole portion)/(average diameter at the communication position of the small-diameter hole portion) is preferably 1.1 to 13, and more preferably 2.5 to 6.5.

The ratio of the depth of the large-diameter hole portion to the depth of the small-diameter hole portion, (the depth of the large-diameter hole portion)/(the depth of the small-diameter hole portion) is preferably 0.005 to 50, more preferably 0.025 to 40.

The method for producing the support used in the present invention is not particularly limited, and a known method can be used.

Hereinafter, the method for producing the support will be described by way of example, but it is needless to say that the method is not limited thereto.

As a method for producing an aluminum support, for example, as a method for producing an aluminum support having an anodic oxide film having micropores extending in a depth direction from a surface on the image recording layer side, a production method in which the following steps are sequentially performed is preferable. (roughening treatment step) of roughening an aluminum plate, (anodic oxidation treatment step) of anodizing the roughened aluminum plate, (hole-expanding treatment step) of bringing the aluminum plate having the anodic oxide film obtained in the anodic oxidation treatment step into contact with an aqueous acid solution or an aqueous alkali solution to expand the diameter of micropores in the anodic oxide film

The steps of each step will be described in detail below.

Roughening treatment Process-

The roughening treatment step is a step of performing roughening treatment including electrochemical roughening treatment on the surface of the aluminum plate. This step is preferably performed before the anodizing step described later, but if the surface of the aluminum plate has a preferable surface shape, this step does not need to be particularly performed.

As for the roughening treatment, only the electrochemical roughening treatment may be performed, but the electrochemical roughening treatment may be performed in combination with the mechanical roughening treatment and/or the chemical roughening treatment.

In the case of combining the mechanical roughening treatment and the electrochemical roughening treatment, it is preferable to perform the electrochemical roughening treatment after the mechanical roughening treatment.

The electrochemical roughening treatment is preferably performed in an aqueous solution mainly containing nitric acid or hydrochloric acid using Direct Current (DC) or Alternating Current (AC).

The method of the mechanical roughening treatment is not particularly limited, but examples thereof include the method described in Japanese patent publication No. 50-040047.

The chemical roughening treatment is not particularly limited, and a known method may be used.

Preferably, after the mechanical roughening treatment, the following chemical etching treatment is performed.

The chemical etching treatment performed after the mechanical roughening treatment is performed for the following purposes: the edge portion of the surface of the aluminum plate having the uneven shape is smoothed to prevent ink adhesion (catching on) at the time of printing, thereby improving the stain-proofing property of the printing plate and removing unnecessary substances such as abrasive particles remaining on the surface.

Examples of the chemical etching treatment include etching using an acid and etching using an alkali, and examples of a method particularly excellent in etching efficiency include a chemical etching treatment using an alkali aqueous solution (hereinafter, also referred to as "alkali etching treatment").

The alkaline agent used in the aqueous alkaline solution is not particularly limited, but examples thereof include caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, and sodium gluconate.

The aqueous base may comprise aluminum ions.

The concentration of the alkaline agent in the aqueous alkaline solution is preferably 0.01% by mass or more, more preferably 3% by mass or more, and preferably 30% by mass or less.

When the alkali etching treatment is performed, it is preferable to perform a chemical etching treatment (hereinafter, also referred to as "desmear treatment") using a low-temperature acidic aqueous solution in order to remove a product generated by the alkali etching treatment.

The acid used in the acidic aqueous solution is not particularly limited, but examples thereof include sulfuric acid, nitric acid, and hydrochloric acid. The temperature of the acidic aqueous solution is preferably 20 to 80 ℃.

As the roughening treatment step, a method of performing the treatment shown in embodiment a or B in the following order is preferable.

The (A) mode-

(2) Chemical etching treatment with an aqueous alkali solution (No. 1 alkaline etching treatment)

(3) Chemical etching treatment (No. 1 desmutting treatment) using an acidic aqueous solution

(4) Electrochemical roughening treatment using an aqueous solution mainly containing nitric acid (No. 1 electrochemical roughening treatment)

(5) Chemical etching treatment using an aqueous alkali solution (2 nd alkaline etching treatment)

(6) Chemical etching treatment (No. 2 desmutting treatment) using an acidic aqueous solution

(7) Electrochemical roughening treatment in aqueous solution mainly containing hydrochloric acid (2 nd electrochemical roughening treatment)

(8) Chemical etching treatment with an aqueous alkali solution (3 rd base etching treatment)

(9) Chemical etching treatment (No. 3 desmutting treatment) using an acidic aqueous solution

The (B mode)

(10) Chemical etching treatment with an aqueous alkali solution (No. 4 alkali etching treatment)

(11) Chemical etching treatment (4 th desmutting treatment) using an acidic aqueous solution

(12) Electrochemical roughening treatment using an aqueous solution mainly containing hydrochloric acid (No. 3 electrochemical roughening treatment)

(13) Chemical etching treatment with an aqueous alkali solution (5 th alkaline etching treatment)

(14) Chemical etching treatment (5 th desmutting treatment) using an acidic aqueous solution

If necessary, (1) mechanical roughening treatment may be performed before the treatment of the above-described mode (2) or before the treatment of the mode (10).

The amount of aluminum plate dissolved in the 1 st and 4 th alkali etching treatments is preferably 0.5g/m²～30g/m²More preferably 1.0g/m²～20g/m²。

The aqueous solution mainly containing nitric acid used in the first electrochemical roughening treatment in the embodiment 1 includes an aqueous solution used in an electrochemical roughening treatment using a direct current or an alternating current. For example, an aqueous solution obtained by adding aluminum nitrate, sodium nitrate, ammonium nitrate or the like to an aqueous solution of 1 to 100g/L nitric acid is exemplified.

Examples of the aqueous solution mainly containing hydrochloric acid used in the electrochemical roughening treatment of the 2 nd electrochemical roughening treatment in the a mode and the 3 rd electrochemical roughening treatment in the B mode include an aqueous solution used in an electrochemical roughening treatment using a direct current or an alternating current. For example, an aqueous solution obtained by adding 0g/L to 30g/L of sulfuric acid to 1g/L to 100g/L of an aqueous hydrochloric acid solution is mentioned. In addition, nitrate ions such as aluminum nitrate, sodium nitrate, and ammonium nitrate may be further added to the solution; hydrochloric acid ions such as aluminum chloride, sodium chloride and ammonium chloride.

As the waveform of the AC power source for the electrochemical roughening treatment, a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, etc. can be used. The frequency is preferably 0.1Hz to 250 Hz.

FIG. 1 is a graph showing an example of an alternate waveform current waveform pattern used in an electrochemical roughening treatment.

In fig. 1, ta is an anodic reaction time, tc is a cathodic reaction time, tp is a time until the current reaches a peak from 0, Ia is a current at the peak on the anodic cycle side, and Ic is a current at the peak on the cathodic cycle side. In the trapezoidal wave, the time tp until the current reaches the peak from 0 is preferably 1msec to 10 msec. The conditions for one cycle of alternating current for electrochemical roughening are preferably: the ratio tc/ta of the anodic reaction time ta to the cathodic reaction time tc of the aluminum plate is 1 to 20, the ratio Qc/Qa of the electric quantity Qc when the aluminum plate is anodic to the electric quantity Qa when the aluminum plate is anodic is 0.3 to 20, and the anodic reaction time ta is in the range of 5msec to 1,000 msec. About electricity The current density, the current peak of the trapezoidal wave, Ia on the anode cycle side and Ic on the cathode cycle side are preferably 10 to 200A/dm². The Ic/Ia is preferably 0.3-20. The total amount of electricity participating in the anode reaction of the aluminum plate at the time point of completion of the electrochemical roughening is preferably 25C/dm²～1,000C/dm²。

The apparatus having the structure shown in fig. 2 can be used in the electrochemical roughening treatment using alternating current.

Fig. 2 is a side view showing an example of radial cells in the electrochemical roughening treatment using alternating current.

In fig. 2, 50 is a main electrolytic bath, 51 is an ac power supply, 52 is a radial drum, 53a and 53b are main electrodes, 54 is an electrolyte supply port, 55 is an electrolyte, 56 is a slit, 57 is an electrolyte passage, 58 is an auxiliary anode, 60 is an auxiliary anode bath, and W is an aluminum plate. When 2 or more electrolytic cells are used, the electrolysis conditions may be the same or different.

The aluminum sheet W is wound around a radial drum 52 disposed by being immersed in the main electrolytic bath 50, and is subjected to electrolytic treatment by a main electrode 53a and a main electrode 53b connected to an ac power supply 51 during conveyance. The electrolyte 55 passes through the slit 56 from the electrolyte supply port 54 and is supplied to the electrolyte passage 57 between the radial drum roller 52 and the main poles 53a and 53 b. The aluminum sheet W treated in the main electrolytic bath 50 is then subjected to electrolytic treatment in the auxiliary anode bath 60. In the auxiliary anode tank 60, an auxiliary anode 58 is disposed to face the aluminum plate W, and the electrolyte 55 is supplied so as to flow through a space between the auxiliary anode 58 and the aluminum plate W.

The amount of aluminum plate dissolved in the 2 nd alkali etching treatment is preferably 1.0g/m from the viewpoint of ease of production of a predetermined original printing plate²Above, more preferably 2.0g/m²～10g/m²。

From the viewpoint of easy production of a predetermined original printing plate, the amount of aluminum plate dissolved in the 3 rd and 4 th alkali etching treatments is preferably 0.01g/m²～0.8g/m²More preferably 0.05g/m²～0.3g/m²。

In the chemical etching treatment (1 st to 5 th desmutting treatments) using an acidic aqueous solution, an acidic aqueous solution containing phosphoric acid, nitric acid, sulfuric acid, chromic acid, hydrochloric acid, or a mixed acid containing two or more of them can be preferably used.

The acid concentration of the acidic aqueous solution is preferably 0.5 to 60% by mass.

Anodic oxidation treatment procedure

The step of the anodizing treatment step is not particularly limited as long as the above-described micropores can be obtained, and known methods can be exemplified.

In the anodizing treatment step, an aqueous solution of sulfuric acid, phosphoric acid, oxalic acid, or the like can be used as an electrolytic cell. For example, the concentration of sulfuric acid is 100g/L to 300 g/L.

The conditions for the anodic oxidation treatment may be appropriately set depending on the electrolyte used, but examples thereof include a liquid temperature of 5 to 70 ℃ (preferably 10 to 60 ℃), and a current density of 0.5A/dm ²～60A/dm²(preferably 5A/dm)²～60A/dm²) A voltage of 1V to 100V (preferably 5V to 50V), an electrolysis time of 1 second to 100 seconds (preferably 5 seconds to 60 seconds), and a coating amount of 0.1g/m²～5g/m²(preferably 0.2 g/m)²～3g/m²)。

Reaming treatment

The pore-enlarging treatment is a treatment (pore diameter-enlarging treatment) for enlarging the diameter (pore diameter) of micropores present in the anodic oxide film formed in the anodic oxidation treatment step.

The pore-enlarging treatment can be performed by contacting the aluminum plate obtained in the anodic oxidation treatment step with an aqueous acid solution or an aqueous alkali solution. The method of contacting is not particularly limited, and examples thereof include a dipping method and a spraying method.

The support may be provided with a back coat layer containing an organic polymer compound described in Japanese patent application laid-open No. 5-045885 and a silicon alkoxide compound described in Japanese patent application laid-open No. 6-035174 on the back surface as required.

A lithographic printing plate precursor as one embodiment of the printing original plate according to the present invention is described below.

[ original plate of lithographic printing plate ]

The lithographic printing plate precursor according to the present invention has an image recording layer on the printing surface side of the support. The lithographic printing plate precursor may have an undercoat layer between the support and the image-recording layer, and a protective layer on the image-recording layer, as required. The image recording layer or the protective layer in the lithographic printing plate precursor is a layer corresponding to the layer containing particles in the printing plate precursor.

< image recording layer >

The image-recording layer of the lithographic printing plate precursor preferably contains an infrared absorber, a polymerization initiator, a polymerizable compound and a polymer compound. The polymer compound may function as a binder polymer of the image recording layer, or may be present in the image recording layer as a particle-shaped polymer compound.

The polymer compound is preferably a polymer compound containing styrene and/or acrylonitrile as a constituent unit.

Examples of the styrene include styrene, p-methylstyrene, p-methoxystyrene, β -methylstyrene, p-methyl- β -methylstyrene, α -methylstyrene, p-methoxy- β -methylstyrene and the like, with styrene being preferred.

The acrylonitrile includes (meth) acrylonitrile and the like, and acrylonitrile is preferred.

According to a preferred embodiment of the lithographic printing plate precursor according to the present invention, the image-recording layer is an image-recording layer containing an infrared absorber, a polymerization initiator, a polymerizable compound, and a binder polymer (hereinafter also referred to as "image-recording layer a").

According to another preferred embodiment of the lithographic printing plate precursor according to the present invention, the image recording layer is an image recording layer containing an infrared absorber, a polymerization initiator, a polymerizable compound, and a particle-shaped polymer compound (hereinafter, also referred to as "image recording layer B").

According to a preferred embodiment of the lithographic printing plate precursor according to the present invention, the image-recording layer is an image-recording layer containing an infrared absorber and thermoplastic polymer particles (hereinafter also referred to as "image-recording layer C").

(image recording layer A)

The image recording layer a contains an infrared absorber, a polymerization initiator, a polymerizable compound, and a binder polymer. The constituent components of the image recording layer a will be described below.

(Infrared absorber)

The infrared absorber has a function of converting absorbed infrared rays into heat and a function of being excited by infrared rays and transferring electrons and/or energy to a polymerization initiator described later. The infrared absorber used in the present invention is preferably a dye or pigment having an absorption maximum at a wavelength of 760nm to 1200nm, and more preferably a dye.

As the dye, the dyes described in paragraphs 0082 to 0088 of Japanese patent application laid-open No. 2014-104631 can be used.

The average particle diameter of the pigment is preferably 0.01 to 1 μm, more preferably 0.01 to 0.5. mu.m. In the case of dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Details are described in "recent pigment application technology" (published by CMC, journal of 1986) and the like.

The infrared absorber may be used in only 1 kind, or two or more kinds may be used simultaneously.

The content of the infrared absorber is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass, and particularly preferably 0.2 to 10% by mass, relative to the total mass of the image recording layer.

(polymerization initiator)

The polymerization initiator is a compound that initiates and accelerates polymerization of the polymerizable compound. As the polymerization initiator, a known thermal polymerization initiator, a compound having a bond with a small bond dissociation ability, a photopolymerization initiator, or the like can be used. Specifically, the radical polymerization initiators described in paragraphs 0092 to 0106 of Japanese patent application laid-open No. 2014-104631 can be used.

Among the polymerization initiators, onium salts are preferable. Among them, an iodonium salt and a sulfonium salt are particularly preferable. Preferred specific compounds for each salt are the same as those described in paragraphs 0104 to 0106 of Japanese patent application laid-open No. 2014-104631.

The content of the polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 0.8 to 20% by mass, relative to the total mass of the image recording layer. In this range, more excellent sensitivity and more excellent stain resistance of non-image portions during printing can be obtained.

[ polymerizable Compound-2 ]

The polymerizable compound is an addition polymerizable compound having at least one ethylenically unsaturated bond, and is preferably selected from compounds having at least one terminal ethylenically unsaturated bond, and more preferably selected from compounds having two or more terminal ethylenically unsaturated bonds. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers or mixtures thereof.

Examples of the monomer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides thereof, and preferably, esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds are used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group with monofunctional or polyfunctional isocyanates or epoxies, dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, and the like are preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate group or epoxy group with monofunctional or polyfunctional alcohols, amines and thiols are preferable, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituent groups such as halogen group or tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols are more preferable.

As another example, a compound group in which an unsaturated phosphonic acid, styrene, vinyl ether, or the like is substituted for the unsaturated carboxylic acid can be used. These are described in reference documents including Japanese patent application laid-open Nos. 2006-508380, 2002-287344, 2008-256850, 2001-342222, 9-179296, 9-179297, 9-179298, 2004-294935, 2006-243493, 2002-275129, 2003-064130, 2003-280187 and 10-333321.

Specific examples of the ester monomer of the polyol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, 1, 3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, ethylene oxide isocyanurate (EO) -modified triacrylate, and polyester acrylate oligomer. Examples of the methacrylate include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, neopentyltetraol trimethacrylate, bis [ p- (3-methacryloyloxy-2-hydroxypropoxy) phenyl ] dimethylmethane, bis [ p- (methacryloyloxyethoxy) phenyl ] dimethylmethane, and the like. Specific examples of the amide monomer of the polyvalent amine compound and the unsaturated carboxylic acid include methylene bisacrylamide, methylene bismethacrylamide, 1, 6-hexamethylene bisacrylamide, 1, 6-hexamethylene bismethacrylamide, diethylenetriamine triacrylate, xylylene bisacrylamide, and diphenylene bismethacrylamide.

Urethane addition polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group are also preferable, and specific examples thereof include vinyl urethane compounds containing 2 or more polymerizable vinyl groups in 1 molecule obtained by adding a polyisocyanate compound having 2 or more isocyanate groups in 1 molecule and a hydroxyl group-containing vinyl monomer represented by the following formula (b) as described in japanese patent publication No. 48-041708.

CH₂＝C(R_b4)COOCH₂CH(R_b5)OH (b)

Wherein R is_b4And R_b5Represents a hydrogen atom or a methyl group.

Such as urethane acrylates described in Japanese patent laid-open Nos. 51-037193, 2-032293, 2-016765, 2003-344997 and 2006-065210, or Japanese patent laid-open Nos. 58-049860, 56-017654 and 62-039417, urethane acrylate compounds having an ethylene oxide skeleton as described in Japanese patent publication No. 62-039418, Japanese patent publication No. 2000-250211 and Japanese patent publication No. 2007-094138, and urethane acrylate compounds having a hydrophilic group as described in U.S. Pat. No. 7153632, Japanese patent application No. 8-505958, Japanese patent publication No. 2007-293221 and Japanese patent publication No. 2007-293223 are also preferable.

Among the above, an isocyanurate ethylene oxide-modified acrylate compound and a compound having a urethane bond or a urea bond in the molecule are particularly preferable from the viewpoint of excellent balance between hydrophilicity relating to developability and polymerization ability relating to printing durability.

The polymerizable compound may be used alone in 1 kind, or two or more kinds may be used simultaneously.

Details of the structure, the single use or the simultaneous use, the method of using the amount of addition, and the like of the polymerizable compound can be arbitrarily set in accordance with the design of the properties of the final lithographic printing plate precursor.

The content of the polymerizable compound is preferably 5 to 75 mass%, more preferably 10 to 70 mass%, and particularly preferably 15 to 60 mass% with respect to the total mass of the image recording layer.

(adhesive Polymer)

The binder polymer is mainly used for the purpose of improving the film strength of the image recording layer. The binder polymer may be a conventionally known polymer, and is preferably a polymer having a film property. Among them, acrylic resins, polyvinyl acetal resins, polyurethane resins, and the like are preferable.

As a preferable binder polymer, there is a polymer having a crosslinkable functional group for improving the film strength of an image portion in a main chain or a side chain as described in japanese patent application laid-open No. 2008-195018, and a polymer having a side chain is preferable. Crosslinking is formed between polymer molecules by the crosslinkable group, and curing is promoted.

The crosslinkable functional group is preferably an ethylenically unsaturated group such as a (meth) acrylic group, a vinyl group, an allyl group, or a styryl group, or an epoxy group, and the crosslinkable functional group can be introduced into the polymer by a polymer reaction or copolymerization. For example, a reaction of an acrylic polymer or polyurethane having a carboxyl group in a side chain thereof with glycidyl methacrylate, or a reaction of a polymer having an epoxy group with a carboxylic acid having an ethylenically unsaturated group such as methacrylic acid can be used.

The content of the crosslinkable group in the binder polymer is preferably 0.1 to 10.0mmol, more preferably 0.25 to 7.0mmol, and particularly preferably 0.5 to 5.5mmol per 1g of the binder polymer.

Also, the binder polymer preferably has a hydrophilic group. The hydrophilic group contributes to imparting on-press developability to the image recording layer. In particular, by allowing a crosslinkable group and a hydrophilic group to coexist, printing durability and on-press developability can be achieved at the same time.

Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, an alkylene oxide structure, an amino group, an ammonium group, an amide group, a sulfo group, a phosphate group, and the like. Among them, an alkylene oxide structure having 1 to 9 alkylene oxide units having 2 or 3 carbon atoms is preferable. When the hydrophilic group is imparted to the adhesive polymer, it can be performed, for example, by copolymerizing a monomer having a hydrophilic group.

In order to control the ink affinity, a lipophilic group such as an alkyl group, an aryl group, an aralkyl group, or an alkenyl group may be introduced into the binder polymer. For example, the polymerization can be carried out by copolymerizing a lipophilic group-containing monomer such as alkyl methacrylate.

The binder polymer preferably has a mass average molecular weight (Mw) of 2,000 or more, more preferably 5,000 or more, and still more preferably 10,000 to 300,000.

The content of the binder polymer is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, and further preferably 10 to 70% by mass, relative to the total mass of the image recording layer.

Preferable examples of the binder polymer include a polymer compound having a polyoxyalkylene chain in a side chain. By containing a polymer compound (hereinafter, also referred to as "POA chain-containing polymer compound") having a polyoxyalkylene chain in a side chain, the penetration of the fountain solution is promoted and the on-press developability is improved in the image recording layer.

Examples of the resin constituting the main chain of the POA chain-containing polymer compound include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylic resins, polystyrene resins, novolac-type phenol resins, polyester resins, synthetic rubbers, natural rubbers, and the like, and acrylic resins are particularly preferable.

In the present invention, the "main chain" represents a relatively longest connecting chain among molecules of the polymer compound constituting the resin, and the "side chain" represents a molecular chain branched from the main chain.

The POA chain-containing polymer compound is a compound substantially not containing a perfluoroalkyl group. "substantially not containing a perfluoroalkyl group" means that the polymer compound contains less than 0.5% by mass of fluorine atoms present as perfluoroalkyl groups, and preferably contains no fluorine atoms. The mass ratio of fluorine atoms can be determined by elemental analysis.

And, the "perfluoroalkyl group" is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.

The alkylene oxide (oxyalkylene) in the polyoxyalkylene chain is preferably an alkylene oxide having 2 to 6 carbon atoms, more preferably ethylene oxide (oxyethylene) or propylene oxide (oxypropylene), and still more preferably ethylene oxide.

The number of repetitions of the polyoxyalkylene chain, i.e., the alkylene oxide in the polyalkylene oxide site, is preferably 2 to 50, more preferably 4 to 25.

When the number of repetitions of the alkylene oxide is 2 or more, the permeability of the fountain solution can be sufficiently improved, and when the number of repetitions is 50 or less, the printing durability is not lowered by abrasion, which is preferable.

The polyalkylene oxide moiety is preferably a structure described in paragraphs 0060 to 0062 of Japanese patent application laid-open No. 2014-104631.

The POA chain-containing polymer compound may have a crosslinking property in order to improve the film strength of the image portion. A POA chain-containing polymer compound having crosslinking properties is described in paragraphs 0063 to 0072 of Japanese patent application laid-open No. 2014-104631.

The ratio of the repeating unit having a poly (alkylene oxide) site to the total repeating unit constituting the POA chain-containing polymer compound is not particularly limited, but is preferably 0.5 to 80 mol%, more preferably 0.5 to 50 mol%. Specific examples of the POA chain-containing polymer compound include those described in paragraphs 0075 to 0076 of jp 2014-104631 a.

If necessary, hydrophilic polymer compounds such as polyacrylic acid and polyvinyl alcohol described in jp 2008-195018 a can be used in combination with the POA chain-containing polymer compound. Further, the lipophilic polymer compound and the hydrophilic polymer compound can be used simultaneously.

The form of the POA chain-containing polymer compound in the image recording layer is as follows: the binder may be present in the form of particles in addition to the binder that functions to connect the components of the image recording layer. When present in the form of particles, the average particle diameter is preferably in the range of 10nm to 1,000nm, more preferably in the range of 20nm to 300nm, and particularly preferably in the range of 30nm to 120 nm.

The content of the POA chain-containing polymer compound is preferably 3 to 90% by mass, more preferably 5 to 80% by mass, based on the total mass of the image recording layer. Within the above range, the ink can more reliably achieve both the permeability of the fountain solution and the image formability.

Another preferable example of the binder polymer is a polymer compound (hereinafter, also referred to as a star polymer compound) having a polymer chain which has a core composed of a polyfunctional thiol having 6 to 10 functions and bonded to the core through a thioether bond and has a polymerizable group. As the star polymer compound, for example, a compound described in Japanese patent laid-open No. 2012-148555 can be preferably used.

The star polymer compound includes a compound having a polymerizable group such as an ethylenically unsaturated bond in a main chain or a side chain, preferably a side chain, for improving the film strength of an image portion as described in jp 2008-195018 a. The polymerizable group forms a crosslink between polymer molecules and accelerates curing.

The polymerizable group is preferably an ethylenically unsaturated group such as a (meth) acrylic group, a vinyl group, an allyl group, or a styryl group, or an epoxy group, and from the viewpoint of polymerization reactivity, a (meth) acrylic group, a vinyl group, or a styryl group is more preferable, and a (meth) acrylic group is particularly preferable. These groups can be introduced into the polymer by a high molecular reaction or copolymerization. For example, a reaction of a polymer having a carboxyl group in a side chain thereof with glycidyl methacrylate or a reaction of a polymer having an epoxy group with an ethylenically unsaturated group-containing carboxylic acid such as methacrylic acid can be used. These groups may be used simultaneously.

The content of the crosslinkable group in the star polymer compound is preferably 0.1mmol to 10.0mmol, more preferably 0.25mmol to 7.0mmol, and particularly preferably 0.5 mmol to 5.5mmol per 1g of the star polymer compound.

Further, the star polymer compound preferably further has a hydrophilic group. The hydrophilic group contributes to imparting on-press developability to the image recording layer. In particular, by allowing a polymerizable group and a hydrophilic group to coexist, printing durability and developability can be achieved at the same time.

As the hydrophilic group, there may be mentioned-SO₃M¹、-OH、-CONR¹R²(M¹Represents a hydrogen atom, a metal ion, an ammonium ion or a phosphonium ion, R¹And R²Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. R¹And R²May be bonded to form a ring. ) -N⁺R³R⁴R⁵X^-(R³～R⁵Each independently represents an alkyl group having 1 to 8 carbon atoms, X^-Represents a counter anion. ) - (CH)₂CH₂O)_nR and- (C)₃H₆O)_mR。

In the formula, n and m independently represent an integer of 1 to 100, and R independently represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

Here, the star polymer compound has a polyoxyalkylene chain (e.g., - (CH) in a side chain₂CH₂O)_nR and- (C)₃H₆O)_mIn the case of the star polymer compound of R), the star polymer compound is a polymer compound having the above polyoxyalkylene chain in a side chain.

Of these hydrophilic groups, -CONR is preferred¹R²、-(CH₂CH₂O)_nR or- (C)₃H₆O)_mR, more preferably-CONR¹R²Or- (CH)₂CH₂O)_nR, particularly preferably- (CH)₂CH₂O)_nAnd R is shown in the specification. And, - (CH)₂CH₂O)_nIn R, n is more preferably 1 to 10, particularly preferably 1 to 4. R is more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom or a methyl group. Two or more of these hydrophilic groups may be used simultaneously.

The star polymer compound preferably has substantially no carboxylic acid group, phosphoric acid group, or phosphonic acid group. Specifically, it is preferably less than 0.1mmol/g, more preferably less than 0.05mmol/g, and particularly preferably 0.03mmol/g or less. When these acid groups are less than 0.1mmol/g, the developability is further improved.

Further, in order to suppress the ink-staining property, a lipophilic group such as an alkyl group, an aryl group, an aralkyl group, or an alkenyl group may be introduced into the star polymer compound. Specifically, a lipophilic group-containing monomer such as alkyl methacrylate may be copolymerized.

Specific examples of the star polymer compound include those described in paragraphs 0153 to 0157 of Japanese patent application laid-open No. 2014-104631.

When the polyfunctional thiol compound is present, the star polymer compound can be synthesized by a known method such as free polymerization of the monomer constituting the polymer chain.

The mass average molecular weight of the star polymer compound is preferably 5,000 to 500,000, more preferably 10,000 to 250,000, and particularly preferably 20,000 to 150,000. Within this range, on-press developability and printing durability become better.

The star polymer compound may be used alone in 1 kind or in combination of two or more kinds. Further, it can be used together with a normal linear binder polymer.

The content of the star polymer compound is preferably 5 to 95% by mass, more preferably 10 to 90% by mass or less, and particularly preferably 15 to 85% by mass or less, based on the total mass of the image recording layer.

In particular, the star polymer compound described in jp 2012-148555 a is preferable in that the penetration of the fountain solution is promoted and the on-press developability is improved.

(other Components)

The image recording layer a may contain other components described below as necessary.

(1) Low molecular hydrophilic compounds

The image recording layer may contain a low-molecular hydrophilic compound in order to improve on-press developability without reducing printing durability.

Examples of the low-molecular hydrophilic compound include water-soluble organic compounds such as glycols and ether or ester derivatives thereof, e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, polyhydric alcohols such as glycerol, pentaerythritol, and tris (2-hydroxyethyl) isocyanurate, organic amines and salts thereof, e.g., triethanolamine, diethanolamine, and monoethanolamine, organic sulfonic acids and salts thereof, e.g., alkylsulfonic acids and salts thereof, organic sulfonic acids and salts thereof, e.g., alkylsulfuric acids and salts thereof, e.g., phenylphosphonic acids and salts thereof, e.g., tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid, and amino acids and salts thereof, and betaines.

Among these, at least one compound selected from the group consisting of polyols, organic sulfates, organic sulfonates and betaines is preferably contained.

Specific examples of the organic sulfonate include compounds described in paragraphs 0026 to 0031 of Japanese patent application laid-open No. 2007-276454 and paragraphs 0020 to 0047 of Japanese patent application laid-open No. 2009-154525. The salt can be potassium salt or lithium salt.

Examples of the organic sulfates include compounds described in paragraphs 0034 to 0038 of Japanese patent application laid-open No. 2007-276454.

The betaine is preferably a compound having 1 to 5 carbon atoms in the hydrocarbon substituent of the nitrogen atom, and specific examples thereof include trimethylammonium acetate, dimethylpropylammonium acetate, 3-hydroxy-4-trimethylammonium butyrate, 4- (1-pyridyl) butyrate, 1-hydroxyethyl-1-imidazolium acetate, trimethylammonium methanesulfonate, dimethylpropylammonium methanesulfonate, 3-trimethylammonium-1-propanesulfonate, and 3- (1-pyridyl) -1-propanesulfonate.

Since the low-molecular hydrophilic compound has a small structure of the hydrophobic portion, the fountain solution does not penetrate into the exposed portion (image portion) of the image recording layer to reduce the hydrophobicity or the film strength of the image portion, and the ink receptivity or the printing durability of the image recording layer can be favorably maintained.

The amount of the low-molecular hydrophilic compound added is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 2 to 10% by mass, based on the total mass of the image recording layer. Within this range, good on-press developability and printing durability can be obtained.

The low-molecular hydrophilic compound may be used alone or in combination of two or more.

(2) Fat-sensing agent

For the purpose of improving the ink-receiving property, a sensitizing agent such as a phosphonium compound, a nitrogen-containing low-molecular-weight compound, or an ammonium group-containing polymer can be used for the image recording layer. In particular, when the protective layer contains an inorganic layered compound, these compounds function as a surface coating agent for the inorganic layered compound and have an effect of preventing a decrease in the ink adhesion during printing due to the inorganic layered compound.

Specific contents of the phosphonium compound, the nitrogen-containing low-molecular-weight compound, and the ammonium group-containing polymer are described in paragraphs 0184 to 0190 of Japanese patent laid-open No. 2014-104631.

The content of the fat-sensitive agent is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 15.0% by mass, and particularly preferably 1 to 10% by mass, based on the total mass of the image recording layer.

(3) Other ingredients

The image recording layer may contain, as other components, a surfactant, a colorant, a printing-out agent, a polymerization inhibitor, a higher fatty acid derivative, a plasticizer, an inorganic particle, an inorganic layered compound, a co-sensitizer, a chain transfer agent, and the like. Specifically, the compounds and the amounts to be added described in paragraphs 0114 to 0159 of Japanese patent application laid-open No. 2008-284817, paragraphs 0023 to 0027 of Japanese patent application laid-open No. 2006-091479, and paragraph 0060 of the specification of U.S. patent application laid-open No. 2008/0311520 can be preferably used.

(formation of image recording layer A)

The image recording layer a is formed by: for example, as described in paragraphs 0142 to 0143 of jp 2008-195018 a, a coating liquid is prepared by dispersing or dissolving the above components as necessary in a known solvent, and the coating liquid is applied to a support directly or through an undercoat layer by a known method such as a bar coater and dried. The amount of the image recording layer (solid content) applied to the support obtained after coating and drying varies depending on the application, but is preferably 0.3g/m²～3.0g/m². Within this range, good sensitivity and good film properties of the image recording layer can be obtained.

An image recording layer B-

The image recording layer B contains an infrared absorber, a polymerization initiator, a polymerizable compound, and a particle-shaped polymer compound. The constituent components of the image recording layer B will be described below.

As the infrared absorber, polymerization initiator and polymerizable compound in the image recording layer B, the infrared absorber, polymerization initiator and polymerizable compound described in the image recording layer a can be used in the same manner.

(Polymer Compound in particle form)

The particle-shaped polymer compound is preferably selected from the group consisting of thermoplastic polymer particles, thermoreactive polymer particles, polymer particles having a polymerizable group, microcapsules containing a hydrophobic compound, and microgels (crosslinked polymer particles). Among them, polymer particles and microgels having a polymerizable group are preferable. In a particularly preferred embodiment, the particle-shaped polymer compound contains at least one ethylenically unsaturated polymerizable group. The presence of such a particle-shaped polymer compound provides an effect of improving printing durability in exposed portions and on-press developability in unexposed portions.

The particle-shaped polymer compound is preferably thermoplastic polymer particles.

As the thermoplastic polymer particles, thermoplastic polymer particles described in, for example, Research Disclosure No.33303, Japanese patent application laid-open No. 9-123387, Japanese patent application laid-open No. 9-131850, Japanese patent application laid-open No. 9-171249, Japanese patent application laid-open No. 9-171250 and European patent application No. 931647, which are published in 1992, are preferable.

Specific examples of the polymer constituting the thermoplastic polymer particles include homopolymers or copolymers of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, vinylcarbazole, and an acrylate or methacrylate having a polyalkylene structure, and mixtures thereof. Preferably, polystyrene, a copolymer containing styrene and acrylonitrile, or polymethyl methacrylate can be used. The thermoplastic polymer particles preferably have an average particle diameter of 0.01 to 3.0. mu.m.

Examples of the thermally reactive polymer particles include polymer particles having a thermally reactive group. The thermally reactive polymer particles form a hydrophobic region by crosslinking based on a thermal reaction and a functional group change at this time.

The thermally reactive group in the polymer particles having a thermally reactive group may be a functional group which can form a chemical bond and which can undergo any reaction, and is preferably a polymerizable group, and examples thereof include an ethylenically unsaturated group (for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.) which undergoes a free polymerization reaction, a cationically polymerizable group (for example, vinyl group, vinyloxy group, epoxy group, oxetanyl group, etc.), an isocyanate group or a block thereof which undergoes an addition reaction, an epoxy group, a vinyloxy group, a functional group having an active hydrogen atom (for example, amino group, hydroxyl group, carboxyl group, etc.) which is a reaction target of these groups, a carboxyl group which undergoes a condensation reaction, a hydroxyl group or an amino group which is a reaction target, an acid anhydride which undergoes a ring-opening addition reaction, an amino group or a hydroxyl group which is a reaction target, and the like.

As described in, for example, japanese patent application laid-open nos. 2001-277740 and 2001-277742, microcapsules contain at least a part of the components of the image recording layer. The constituent components of the image recording layer may be contained outside the microcapsules. A preferable embodiment of the microcapsule-containing image recording layer has a structure in which a hydrophobic constituent is contained in the microcapsule and a hydrophilic constituent is contained outside the microcapsule.

The microgel (crosslinked polymer particles) may contain a part of the constituent components of the image recording layer on at least one of the surface and the inside thereof. In particular, from the viewpoint of image formation sensitivity or printing durability, a reactive microgel having a free polymerizable group on the surface thereof is preferred.

When the constituent components of the image recording layer are microencapsulated or microgeled, a known method can be applied.

Further, as the polymer compound in the particle shape, polymer particles obtained by the reaction of a polyvalent isocyanate compound which is an adduct of a polyvalent phenol compound having 2 or more hydroxyl groups in the molecule and isophorone diisocyanate and a compound having active hydrogen are preferable from the viewpoint of printing durability, antifouling property and storage stability.

The polyphenol compound is preferably a compound having a plurality of benzene rings having a phenolic hydroxyl group.

The compound having the active hydrogen is preferably a polyol compound or a polyamine compound, more preferably a polyol compound, and still more preferably at least one compound selected from the group consisting of propylene glycol, glycerin, and trimethylolpropane.

The resin particles obtained by the reaction of a polyvalent isocyanate compound which is an adduct of a polyvalent phenol compound having 2 or more hydroxyl groups in the molecule and isophorone diisocyanate and a compound having an active hydrogen are preferably polymer particles described in paragraphs 0032 to 0095 in Japanese patent laid-open No. 2012-206495.

In addition, the particle-shaped polymer compound preferably has a hydrophobic main chain and includes both i) a constituent unit having a cyano side group directly bonded to the hydrophobic main chain and ii) a constituent unit having a side group including a hydrophilic polyalkylene oxide segment, from the viewpoint of printing durability and solvent resistance.

The hydrophobic main chain is preferably an acrylic resin chain.

Preferable examples of the cyano side group include- [ CH ] ₂CH(C≡N)-]Or- [ CH ]₂C(CH₃)(C≡N)-]。

Further, the constituent unit having the above cyano side group can be easily derived from an ethylenically unsaturated monomer such as acrylonitrile or methacrylonitrile, or from a combination thereof.

The alkylene oxide in the hydrophilic polyalkylene oxide segment is preferably ethylene oxide or propylene oxide, and more preferably ethylene oxide.

The number of repetition of the alkylene oxide structure in the hydrophilic polyalkylene oxide segment is preferably 10 to 100, more preferably 25 to 75, and still more preferably 40 to 50.

The particles of the resin having a hydrophobic main chain and containing both i) a constitutional unit having a cyano side group directly bonded to the hydrophobic main chain and ii) a constitutional unit having a side group containing a hydrophilic polyalkylene oxide segment are preferably particles described in paragraphs 0039 to 0068 of Japanese patent application laid-open No. 2008-503365.

The average particle diameter of the polymer compound in the form of particles is preferably 0.01 to 3.0. mu.m, more preferably 0.03 to 2.0. mu.m, and still more preferably 0.10 to 1.0. mu.m. Within this range, good resolution and stability over time can be obtained.

The content of the particle-shaped polymer compound is preferably 5 to 90% by mass based on the total mass of the image recording layer.

(other Components)

The image recording layer B may contain other components described in the image recording layer a as needed.

(formation of image recording layer B)

The description of the formation of the image recording layer a can be applied to the formation of the image recording layer B.

An image recording layer C-

The image recording layer C contains an infrared absorber and thermoplastic polymer particles. The constituent components of the image recording layer C will be described below.

(Infrared absorber)

The infrared absorber contained in the image recording layer C is preferably a dye or pigment having an absorption maximum in a wavelength range of 760nm to 1,200 nm. More preferably a dye.

As the dye, there can be used a commercially available dye and a known dye described in a literature (for example, "near infrared absorbing dye" edited by "society for organic synthetic chemistry" in showa 45, journal of showa 45, "chemical industry" in 1986, No. p.45 to 51, development and marketing of a functional dye in 90 s "chapter 2.3 (published by CMC, journal of 1990)), or japanese patent. Specifically, infrared absorbing dyes such as azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, polymethine dyes, and cyanine dyes are preferable.

Among these, particularly preferred dyes to be added to the image recording layer C are infrared absorbing dyes having a water-soluble group.

Specific examples of the infrared absorbing dye are shown below, but the dye is not limited to these.

[ chemical formula 1]

[ chemical formula 2]

As the pigment, commercially available pigments and pigments described in color index (c.i.) overview, "latest pigment overview" (edited by japan pigment technology association, journal of 1977), "latest pigment application technology" (CMC published, journal of 1986), and "printing ink technology" (CMC published, journal of 1984) can be used.

The particle size of the pigment is preferably 0.01 to 1 μm, more preferably 0.01 to 0.5. mu.m. As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Details are described in "recent pigment application technology" (published by CMC, journal of 1986).

The content of the infrared absorber is preferably 0.1 to 30% by mass, more preferably 0.25 to 25% by mass, and particularly preferably 0.5 to 20% by mass, relative to the total mass of the image recording layer. Within the above range, good sensitivity can be obtained without impairing the film strength of the image recording layer.

(thermoplastic Polymer particles)

The thermoplastic polymer particles preferably have a glass transition temperature (Tg) of from 60 ℃ to 250 ℃. The Tg of the thermoplastic polymer particles is more preferably from 70 ℃ to 140 ℃, still more preferably from 80 ℃ to 120 ℃.

As the thermoplastic polymer particles having a Tg of 60 ℃ or higher, for example, preferable particles are those described in, for example, research Disclosure No.33303, Japanese patent application laid-open No. 9-123387, Japanese patent application laid-open No. 9-131850, Japanese patent application laid-open No. 9-171249, Japanese patent application laid-open No. 9-171250 and European patent application laid-open No. 931647 of No. 1.1992.

Specifically, a homopolymer or a copolymer of monomers such as ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile, and vinylcarbazole, or a mixture thereof can be exemplified. Preferable examples thereof include polystyrene, a copolymer containing styrene and acrylonitrile, and polymethyl methacrylate.

From the viewpoint of resolution and stability over time, the average particle diameter of the thermoplastic polymer particles is preferably 0.005 μm to 2.0. mu.m. This value can also be applied as the average particle diameter in the case where two or more thermoplastic polymer particles are mixed. The average particle diameter is more preferably 0.01 to 1.5. mu.m, and particularly preferably 0.05 to 1.0. mu.m. The polydispersity in the case where two or more thermoplastic polymer particles are mixed is preferably 0.2 or more. The average particle diameter and polydispersity can be calculated by laser scattering methods.

Two or more thermoplastic polymer particles may be used in combination. Specifically, at least two types of particles having different particle sizes or at least two types of particles having different Tg may be used. When two or more kinds are used in combination, the film curability of the image portion is further improved, and the printing durability is further improved when the plate is used as a lithographic printing plate.

For example, when particles having the same particle size are used as the thermoplastic polymer particles, pores may be present between the thermoplastic polymer particles to some extent, and even when the thermoplastic polymer particles are melted and solidified by image exposure, the film curability may not be as high as desired. In contrast, when particles having different particle sizes are used as the thermoplastic polymer particles, the porosity between the thermoplastic polymer particles can be reduced, and as a result, the film curability of the image portion after image exposure can be improved.

When particles having the same Tg are used as the thermoplastic polymer particles, if the temperature of the image recording layer is not sufficiently increased by image exposure, the thermoplastic polymer particles are not sufficiently melted and solidified, and the film curability may not be as high as desired. On the other hand, when particles having different Tg are used as the thermoplastic polymer particles, the film curability of the image portion can be improved even if the temperature of the image recording layer is not sufficiently increased by the image exposure.

When two or more thermoplastic polymer particles having different Tg's are used in combination, the Tg of at least one thermoplastic polymer particle is preferably 60 ℃ or higher. In this case, the difference in Tg is preferably 10 ℃ or more, more preferably 20 ℃ or more. The thermoplastic polymer particles preferably contain 70 mass% or more of thermoplastic polymer particles having a Tg of 60 ℃ or higher with respect to all the thermoplastic polymer particles.

The thermoplastic polymer particles may have a crosslinkable group. By using the thermoplastic polymer particles having a crosslinkable group, the crosslinkable group thermally reacts with heat generated in the image-exposed portion to form a crosslink between the polymers, so that the film strength in the image portion is improved and the printing durability is further improved. The crosslinkable group may be a functional group which can form a chemical bond and can be reacted in any manner, and examples thereof include an ethylenically unsaturated group which undergoes a polymerization reaction (for example, acryloyl group, methacryloyl group, vinyl group, allyl group, etc.), an isocyanate group which undergoes an addition reaction or a block thereof, a group having an active hydrogen atom which is a reaction target thereof (for example, amino group, hydroxyl group, carboxyl group, etc.), an epoxy group which likewise undergoes an addition reaction, an amino group, carboxyl group or hydroxyl group which is a reaction target thereof, a carboxyl group and hydroxyl group or amino group which undergo a condensation reaction, an acid anhydride and amino group or hydroxyl group which undergo a ring-opening addition reaction, and the like.

Specific examples of the thermoplastic polymer particles having a crosslinkable group include particles having a crosslinkable group such as an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an acid anhydride, and a group for protecting these groups. The introduction of these crosslinkable groups into the polymer may be carried out at the time of polymerization of the polymer particles, or may be carried out by a polymer reaction after the polymerization of the polymer particles.

When a crosslinkable group is introduced during polymerization of the polymer particles, a monomer having a crosslinkable group is preferably emulsion-polymerized or suspension-polymerized. Specific examples of the monomer having a crosslinkable group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, glycidyl methacrylate, glycidyl acrylate, blocked isocyanate such as 2-isocyanatoethyl methacrylate or an alcohol thereof, blocked isocyanate such as 2-isocyanatoethyl acrylate or an alcohol thereof, 2-aminoethylmethacrylate, 2-aminoethylacrylate, 2-hydroxyethylmethacrylate, 2-hydroxyethylacrylate, acrylic acid, methacrylic acid, maleic anhydride, 2-functional acrylates, 2-functional methacrylates and the like.

Examples of the polymer reaction used when introducing the crosslinkable group after the polymerization of the polymer particles include the polymer reaction described in international publication No. 96/34316.

The thermoplastic polymer particles may be reacted with each other via a crosslinkable group, or may be reacted with a high molecular compound or a low molecular compound added to the image recording layer.

The content of the thermoplastic polymer particles is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and particularly preferably 70 to 85% by mass, relative to the total mass of the image recording layer.

(other Components)

The image recording layer C may contain other components as needed.

As the other component, a surfactant having a polyoxyalkylene group or a hydroxyl group is preferably exemplified.

As the surfactant having a polyoxyalkylene group (hereinafter, also referred to as "POA group") or a hydroxyl group, a surfactant having a POA group or a hydroxyl group can be suitably used, but an anionic surfactant or a nonionic surfactant is preferable. Among anionic surfactants or nonionic surfactants having a POA group or a hydroxyl group, anionic surfactants or nonionic surfactants having a POA group are preferable.

As the POA group, polyoxyethylene group, polyoxypropylene group, polyoxybutenyl group and the like are preferable, and polyoxyethylene group is particularly preferable.

The average polymerization degree of the oxyalkylene group is preferably 2 to 50, more preferably 2 to 20.

The number of hydroxyl groups is preferably 1 to 10, more preferably 2 to 8. However, the terminal hydroxyl group in the oxyalkylene group is not included in the number of hydroxyl groups.

The anionic surfactant having a POA group is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether carboxylates, polyoxyalkylene alkyl sulfosuccinates, polyoxyalkylene alkyl ether sulfates, alkylphenoxypolyallylsulfonates, polyoxyalkylene alkyl sulfophenylethers, polyoxyalkylene aryl ether sulfates, polyoxyalkylene polycyclic phenyl ether sulfates, polyoxyalkylene styrylphenyl ether sulfates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkylphenyl ether phosphates, and polyoxyalkylene perfluoroalkyl ether phosphates.

The anionic surfactant having a hydroxyl group is not particularly limited, and examples thereof include hydroxycarboxylic acid salts, hydroxyalkyl ether carboxylic acid salts, hydroxyalkyl sulfonic acid salts, fatty acid monoglyceride sulfate salts, and fatty acid monoglyceride phosphate salts.

The content of the surfactant having a POA group or a hydroxyl group is preferably 0.05 to 15 mass%, more preferably 0.1 to 10 mass%, with respect to the total mass of the image recording layer.

Specific examples of the surfactant having a POA group or a hydroxyl group are given below, but the surfactant is not limited thereto. Surfactant A-12 described below is the product name ZONYL FSP and is available from Du Pont. Also, surfactant N-11, described below, is the product name ZONYL FSO 100 and is available from Du Pont. In addition, m and n in A-12 each independently represent an integer of 1 or more.

[ chemical formula 3]

[ chemical formula 4]

The image recording layer may contain an anionic surfactant having no polyoxyalkylene group or hydroxyl group for the purpose of ensuring coating uniformity of the image recording layer.

The anionic surfactant is not particularly limited as long as the above object can be achieved. Of these, preferred are alkylbenzenesulfonic acids or salts thereof, alkylnaphthalenesulfonic acids or salts thereof, (di) alkyldiphenylether (di) sulfonic acids or salts thereof, and alkylsulfuric ester salts.

The amount of the anionic surfactant having no polyoxyalkylene group or hydroxyl group added is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on the total mass of the surfactant having a polyoxyalkylene group or hydroxyl group.

Specific examples of anionic surfactants having no polyoxyalkylene group and no hydroxyl group are given below, but the present invention is not limited to these.

[ chemical formula 5]

In addition, for the purpose of ensuring the coating uniformity of the image recording layer, a nonionic surfactant or a fluorine-based surfactant having no polyoxyalkylene group or hydroxyl group may be used. For example, a fluorine-based surfactant described in Japanese patent application laid-open No. 62-170950 is preferably used.

The image recording layer can contain a hydrophilic resin. As the hydrophilic resin, for example, a resin having a hydrophilic group such as a hydroxyl group, a hydroxyethyl group, a hydroxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, a carboxyl group, a carboxylate group, a sulfo group, a sulfonic group, or a phosphoric group is preferable.

Specific examples of the hydrophilic resin include gum arabic, casein, gelatin, starch derivatives, carboxymethylcellulose and sodium salt thereof, cellulose acetate, sodium alginate, vinyl acetate-maleic acid copolymers, styrene-maleic acid copolymers, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and copolymers of hydroxyethyl acrylate, homopolymers and copolymers of hydroxypropyl methacrylate, homopolymers and copolymers of hydroxypropyl acrylate, homopolymers and copolymers of hydroxybutyl methacrylate, homopolymers and copolymers of hydroxybutyl acrylate, polyethylene glycol, hydroxypropylene polymers, polyvinyl alcohols, hydrolyzed polyvinyl acetate having a degree of hydrolysis of preferably at least 60%, more preferably at least 80%, polyvinyl formal, polyvinyl acetate, polyvinyl acetal, polyvinyl acetate, sodium alginate, polyvinyl acetate-maleic acid copolymers, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, homopolymers and copolymers of hydroxyethyl methacrylate, homopolymers and, Polyvinyl butyral, polyvinyl pyrrolidone, homopolymers and copolymers of acrylamide, homopolymers and copolymers of methacrylamide, homopolymers and copolymers of N-methylolacrylamide, and the like.

The mass average molecular weight of the hydrophilic resin is preferably 2,000 or more from the viewpoint of obtaining sufficient film strength and printing durability.

The content of the hydrophilic resin is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, relative to the total mass of the image recording layer.

The image recording layer may contain inorganic particles, unlike for the above-described formation of unevenness. The inorganic particles include silica, alumina, magnesia, titania, magnesium carbonate, calcium alginate, and mixtures thereof, as preferred examples. The inorganic particles can be used for the purpose of strengthening the coating film.

The average particle diameter of the inorganic particles is preferably 5nm to 10 μm, more preferably 10nm to 1 μm. Within this range, the particles can be stably dispersed in the thermoplastic polymer particles, the film strength of the image recording layer is sufficiently maintained, and a non-image portion which is less likely to cause printing stain and has excellent hydrophilicity is formed.

The inorganic particles can be easily obtained as a commercially available product such as a colloidal silica dispersion.

The content of the inorganic particles is preferably 1.0 to 70% by mass, more preferably 5.0 to 50% by mass, relative to the total mass of the image recording layer.

The image recording layer may contain a plasticizer to impart flexibility to the coating film. Examples of the plasticizer include polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, and tetrahydrofurfuryl oleate.

The content of the plasticizer is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, relative to the total mass of the image recording layer.

When polymer particles having a thermally reactive functional group (crosslinkable group) are used in the image recording layer, a compound that initiates or accelerates the reaction of the thermally reactive functional group (crosslinkable group) can be added as necessary. Examples of the compound which initiates or accelerates the reaction of the thermally reactive functional group include compounds which generate, for example, radicals or cations by heat. Examples thereof include onium salts containing a powderine base dimer, a trihalomethyl compound, a peroxide, an azo compound, a diazonium salt, a diphenyliodonium salt and the like, acylphosphines, imide sulfonic acids and the like. The amount of such a compound added is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, relative to the total mass of the image recording layer. Within this range, a good effect of initiating or accelerating the reaction can be obtained without impairing the on-press developability.

(formation of image recording layer C)

The image recording layer C is formed as follows: the coating liquid is prepared by dissolving or dispersing the above-mentioned components as necessary in an appropriate solvent, and is applied to the support directly or via an undercoat layer. As the solvent, water or a mixed solvent of water and an organic solvent can be used, but water and an organic solvent are preferably used in combination from the viewpoint of making the coated sheet good. The amount of the organic solvent is not clearly specified depending on the type of the organic solvent, and is preferably 5 to 50% by volume in the mixed solvent. However, the organic solvent needs to be used in an amount within a range in which the thermoplastic polymer particles are not aggregated. The solid content concentration of the image recording layer coating liquid is preferably 1 to 50% by mass.

The organic solvent used as the solvent of the coating liquid is preferably an organic solvent soluble in water. Specific examples thereof include alcohol solvents such as methanol, ethanol, propanol, isopropanol and 1-methoxy-2-propanol, ketone solvents such as acetone and methyl ethyl ketone, glycol ether solvents such as ethylene glycol dimethyl ether, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and dimethylsulfoxide. In particular, an organic solvent having a boiling point of 120 ℃ or lower and a solubility in water (a dissolved amount of 100g in water) of 10g or more is preferable, and an organic solvent of 20g or more is more preferable.

Various methods can be used as a method of applying the coating liquid for an image recording layer. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating. The amount of the image recording layer (solid content) on the support obtained after coating and drying varies depending on the application, and is preferably 0.5g/m²～5.0g/m²More preferably 0.5g/m²～2.0g/m²。

Other structural requirements of the lithographic printing plate precursor are described below.

< undercoat layer >

In the lithographic printing plate precursor according to the present invention, an undercoat layer may be provided between the image recording layer and the support as necessary. The undercoat layer enhances adhesion between the support and the image recording layer in the exposed portion, and easily causes peeling from the support of the image recording layer in the unexposed portion, thereby contributing to improvement of on-press developability without impairing printing durability. In the case of infrared laser exposure, the undercoat layer functions as a heat-insulating layer, and thus has an effect of preventing sensitivity from being lowered by diffusion of heat generated by exposure to the support.

Specific examples of the compound used for the undercoat layer include a silane coupling agent having an addition-polymerizable ethylenic double bond-reactive group as described in Japanese patent application laid-open No. 10-282679, and a phosphorus compound having an ethylenic double bond-reactive group as described in Japanese patent application laid-open No. 2-304441. As a preferred compound, there can be mentioned a polymer compound having an adsorptive group, a hydrophilic group and a crosslinkable group which can be adsorbed on the surface of the support as described in Japanese patent laid-open Nos. 2005-125749 and 2006-188038. The polymer compound is preferably a copolymer of a monomer having an adsorptive group, a monomer having a hydrophilic group, and a monomer having a crosslinkable group. More specifically, phenolic hydroxyl group, carboxyl group, -PO can be mentioned₃H₂、-OPO₃H₂、-CONHSO₂-、-SO₂NHSO₂-、-COCH₂COCH₃And the like, monomers having an adsorptive group, monomers having a hydrophilic group such as a sulfo group, and the like, and monomers having a polymerizable crosslinkable group such as a methacrylic group, an allyl group, and the like. The polymer compound may have a crosslinkable group introduced by forming a salt of a polar substituent of the polymer compound, a substituent having an opposite charge, and a compound having an ethylenically unsaturated bond. Further, monomers other than the above monomers may be copolymerized, and hydrophilic monomers are preferable.

The content of the ethylenically unsaturated bond in the polymer compound for the undercoat layer is preferably 0.1 to 10.0mmol, more preferably 2.0 to 5.5mmol, per 1g of the polymer compound.

The mass average molecular weight of the polymer compound for the undercoat layer is preferably 5,000 or more, and more preferably 10,000 to 300,000.

The undercoat layer may contain, in addition to the compound for undercoat layer, a chelating agent, a secondary or tertiary amine, a polymerization inhibitor, a compound having an amino group or a functional group having a polymerization inhibiting ability and a group that interacts with the surface of the aluminum support, or the like (for example, 1, 4-diazabicyclo [2.2.2] octane (DABCO), 2,3,5, 6-tetrahydroxy-p-benzoquinone, chloranil, sulfophthalic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, or the like) in order to prevent contamination with the passage of time.

The primer layer can be applied by a known method. The coating amount of the undercoat layer is preferably 0.1mg/m in terms of the coating amount after drying²～100mg/m²More preferably 1mg/m²～30mg/m²。

< protective layer >

The lithographic printing plate precursor according to the present invention may have a protective layer on the image-recording layer. The protective layer has a function of inhibiting an image formation inhibition reaction by blocking oxygen, and also has a function of preventing scratches from being generated in the image recording layer and preventing ablation during exposure to high-illuminance laser light.

As the protective layer having such a function, the protective layer described in paragraphs 0202 to 0204 of japanese patent application laid-open No. 2014-104631 can be used.

The protective layer preferably comprises a water-soluble polymer. Examples of the water-soluble polymer used for the protective layer include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, polyethylene glycol, and poly (meth) acrylonitrile.

As the modified polyvinyl alcohol, an acid-modified polyvinyl alcohol having a carboxyl group or a sulfo group is preferably used. Specifically, modified polyvinyl alcohols described in Japanese patent application laid-open Nos. 2005-250216 and 2006-259137 are mentioned.

Among the water-soluble polymers, polyvinyl alcohol is preferable, and polyvinyl alcohol having a saponification degree of 50% or more is more preferable. The saponification degree of the polyvinyl alcohol is preferably 60% or more, more preferably 70% or more, and still more preferably 85% or more. The upper limit of the saponification degree is not particularly limited, and may be 100% or less.

The degree of saponification can be determined according to JIS K6726: 1994.

The protective layer can be applied by a known method. There may be no protective layer, and in the case where a protective layer is provided on the image recording layer, the film thickness of the protective layer is preferably less than 0.2 μm.

The lithographic printing plate precursor can be produced by coating the coating liquid of each structural layer according to a usual method and drying to form each structural layer. For coating, a die coating method, a dip coating method, an air knife coating method, a curtain coating method, a roll coating method, a wire bar coater coating method, a gravure coating method, a slide coating method, or the like is used.

Hereinafter, a waste printing plate precursor as another embodiment of the printing plate precursor according to the present invention will be described.

The waste printing plate precursor for printing is a precursor for producing a waste printing plate through the same plate making process as the lithographic printing plate precursor (in which image exposure is not performed), and is substantially free of photosensitivity. As is well known in the printing field, the waste printing plate is attached to a plate cylinder and used when, for example, a part of a paper surface needs to be printed with 2 colors or 1 color in color newspaper printing (multicolor printing).

[ waste printing plate precursor for printing ]

The waste printing plate precursor for printing according to the present invention has a non-photosensitive resin layer on the printing surface side of the support. The waste printing plate precursor for printing may have an undercoat layer between the support and the non-photosensitive resin layer, and a hydrophilic layer (also referred to as a protective layer) on the non-photosensitive resin layer, as required. The non-photosensitive resin layer or the hydrophilic layer in the waste printing plate precursor corresponds to the layer containing particles in the printing plate precursor.

The non-photosensitive resin layer in the waste plate precursor for printing preferably contains a water-soluble binder polymer or a water-insoluble and alkali-soluble binder polymer (hereinafter, also referred to as "binder polymer"). The non-photosensitive resin layer can contain a colorant having a maximum absorption at 350 to 800nm and a low-molecular acidic compound.

The binder contained in the non-photosensitive resin layer in the waste plate precursor for printing is described in, for example, paragraph [ 0069 ] - [ 0074 ] of japanese patent laid-open No. 2012-218778.

The non-photosensitive resin layer in the waste plate precursor for printing and the method for forming the same are described in, for example, paragraphs [ 0021 ] - [ 0054 ] of Japanese patent laid-open No. 2012-218778.

The hydrophilic layer in the waste printing plate precursor for printing contains a binder. The hydrophilic layer can be formed by applying a hydrophilic layer coating solution prepared by stirring and mixing a binder and various additives such as a colorant, a water-soluble plasticizer, and a surfactant, which are added according to the purpose, onto the non-photosensitive layer by applying a method described in, for example, U.S. Pat. No. 3,458,311 or jp 55-049729 a.

The binder contained in the hydrophilic layer in the waste printing plate precursor for printing is described in, for example, paragraph [ 0069 ] - [ 0074 ] of japanese patent laid-open No. 2012-218778.

[ original plate laminate for printing ]

The printing original plate laminate according to the present invention is a laminate obtained by laminating the printing original plates according to the present invention, and is preferably a laminate obtained by laminating a plurality of printing original plates according to the present invention, and laminating the outermost layer on the printing surface side and the outermost layer on the side opposite to the printing surface side in direct contact with each other.

The printing original plate laminate according to the present invention is preferably a laminate in which a plurality of printing original plates according to the present invention are laminated without interleaving paper.

The number of stacked sheets is not particularly limited, but is preferably 2 to 500 sheets.

The original printing plate laminate according to the present invention has excellent properties of preventing multiple feeding and scratching, and is less likely to cause register shift, because of the properties of the original printing plate according to the present invention.

[ method of making plate for printing plate and printing method ]

The method for making a printing plate according to the present invention is not particularly limited as long as it is a method for making a printing plate precursor according to the present invention, but is preferably a method for making a printing plate using a printing plate precursor according to the present invention, the method including: a step of exposing an image to the printing original plate according to the present invention (also referred to as an "image exposure step"); and a step of producing a printing plate by supplying at least one of a printing ink and a fountain solution and removing the unexposed portion of the image recording layer on the printing machine (also referred to as a "development treatment step"). In the printing original plate according to the present invention, the printing waste original plate is subjected to a development treatment step without undergoing an image exposure step. In the developing treatment step, the non-photosensitive resin layer is removed.

Hereinafter, the above-described plate making method is also referred to as an "on-press development system".

The printing method according to the present invention is a method for producing and printing a printing plate using the printing original plate according to the present invention, and preferably includes: a step of exposing an image to the printing original plate according to the present invention (also referred to as an "image exposure step"); a step of producing a printing plate by supplying at least one of a printing ink and a fountain solution and removing an unexposed portion of the image recording layer on a printing machine (also referred to as a "development treatment step"); and a step of printing using the obtained printing plate (also referred to as a "printing step"). In the printing original plate according to the present invention, the printing waste original plate is subjected to a development treatment step without undergoing an image exposure step.

< image Exposure Process >

The image exposure of the printing original plate can be performed in accordance with an image exposure operation of a general lithographic printing plate original plate.

The image exposure is performed by laser exposure through transparent original having a line image, a halftone image, or the like, or by laser scanning based on digital data, or the like. A light source having a wavelength of 700nm to 1,400nm is preferably used. As the light source of 700nm to 1,400nm, solid-state lasers and semiconductor lasers radiating infrared rays are preferable. The infrared laser preferably has an output of 100mW or more, an exposure time per 1 pixel of 20 microseconds or less, and irradiation energy of 10mJ/cm ²～300mJ/cm². In order to shorten the exposure time, a multi-beam laser apparatus is preferably used. The exposure mechanism may be any of an inner drum system, an outer drum system, a flat plate system, and the like. The image exposure can be performed by a conventional method using a plate setter or the like.

< development processing step >

The development treatment can be performed by a usual method. In the case of on-press development, when at least either one of a fountain solution and a printing ink is supplied onto a printing press to the image-exposed printing original plate, a printing ink containing portion having an oleophilic surface is formed in the exposed portion of the image recording layer from the image recording layer cured by exposure. On the other hand, in the unexposed portion, the uncured image recording layer is removed by dissolution or dispersion by at least either of the supplied fountain solution and printing ink, and the hydrophilic surface is exposed in the portion. As a result, the fountain solution adheres to the exposed hydrophilic surface, and the printing ink is applied to the image recording layer in the exposed region to start printing.

Here, the fountain solution may be supplied to the surface of the original printing plate or the printing ink at first, but it is preferable to supply the fountain solution at first in order to permeate the fountain solution and promote the on-press developability.

< printing Process >

Printing using the resulting printing plate can be performed by a usual method. Desired printing ink and a dampening solution as needed can be supplied to the printing plate to perform printing.

The supply amount of the printing ink and the fountain solution is not particularly limited, and may be appropriately set according to the desired printing.

The method of supplying the printing ink and the dampening solution to the printing plate is not particularly limited, and can be performed by a known method.

The lithographic printing plate precursor according to the present invention can be used to produce a lithographic printing plate by a developing treatment using a developer, with an appropriate selection of a binder polymer or the like as a constituent of the image recording layer.

Another embodiment of the plate making method of a printing plate according to the present invention preferably includes: a step of exposing an image to the printing original plate according to the present invention (also referred to as an "image exposure step"); and a developing step (also referred to as a "developer developing step") of supplying a developer having a pH of 2 or more and 14 or less to remove the unexposed portions.

Hereinafter, the plate making method is also referred to as a "developer solution processing method".

Another aspect of the printing method according to the present invention is a method of producing a printing plate using the printing original plate according to the present invention and printing, preferably including: a step of exposing an image to the printing original plate according to the present invention (also referred to as an "image exposure step"); a developing step of supplying a developer having a pH of 2 or more and 14 or less to remove the unexposed portions (also referred to as a "developer developing step"); and a step of printing using the obtained printing plate (also referred to as a "printing step").

< image Exposure Process >

The image exposure process in the developer processing method is the same as the image exposure process in the on-press development method described above.

< developing step with developer solution >

The development treatment using a developer includes a method including a step of supplying a developer having a pH of 2 or more and 12 or less to remove an unexposed portion of the image recording layer (also referred to as a simple development treatment). The developer having a pH of 2 or more and 12 or less may contain at least one compound selected from the group consisting of a surfactant and a water-soluble polymer compound.

Further, a method including a step of supplying a developer having a pH of 2 or more and 10 or less to remove an unexposed portion of the image recording layer, and not including a water washing step after the unexposed portion removing step is also a preferable mode of the simple development treatment.

The developing and the gum solution treatment steps can be performed simultaneously by a method in which a water-soluble polymer compound or the like is contained in the developer as necessary.

Therefore, particularly, the post-washing step is not required, and the drying step can be performed after the development and the gum solution treatment in the 1-liquid-1 step. Accordingly, as the development treatment using the developer, a method for producing a printing plate including a step of developing the printing original plate after the image exposure by the developer having a pH of 2 or more and 12 or less is preferable. After the development treatment, it is preferable to perform drying after removing the remaining developer using a squeegee roller.

That is, in the developing step of the method for producing a printing plate according to the present invention, it is preferable to perform the developing treatment and the gum solution treatment in the 1-liquid-1 step.

The developing and gum solution treatment in the 1-liquid-1 step means that the developing treatment and gum solution treatment are performed in the 1-step with the 1-liquid without performing the developing treatment and gum solution treatment as separate steps.

The developing process can be preferably performed by an automatic developing processor including a supply mechanism of the developer and a friction member. As the rubbing member, an automatic developing processor using a rotating brush roller is particularly preferable.

The number of the rotating brush rolls is preferably 2 or more. The automatic development processor preferably includes a mechanism for removing excess developer such as a squeegee roller or a drying mechanism such as a heater after the development processing mechanism. The automatic development processor preferably includes a pre-heating mechanism for performing a heating process on the lithographic printing plate precursor after the image exposure, before the development processing mechanism.

The process based on such an automatic development processor has the following advantages: in the case of an image recording layer, a non-photosensitive resin layer, and a protective layer, which are generated in the case of a so-called on-press development treatment, the development residue derived from the protective layer can be released from the countermeasure.

In the case of a manual process in the development, a preferred method of the development treatment is, for example, a method in which an aqueous solution is contained in sponge, cotton wool, or the like, the entire surface of the plate is rubbed while the treatment is performed, and the plate is dried after the treatment is completed. In the case of the dipping treatment, for example, a method of dipping the printing original plate in a vat or a deep tank containing an aqueous solution for about 60 seconds and stirring the solution, and then drying the solution by rubbing the solution with cotton wool or sponge or the like is preferable.

In the developing treatment, an apparatus having a simplified structure and simplified steps is preferably used.

For example, in the alkali development treatment, the protective layer is removed by a pre-water washing step, followed by development with a high-pH alkaline developer, followed by alkali removal by a post-water washing step, glue treatment by a glue application step, and drying by a drying step. In the simple development treatment, development and gumming can be simultaneously performed with 1 liquid. Therefore, the post-washing step and the gum treatment step can be omitted, and it is preferable to perform the drying step as needed after performing development and gumming (gum solution treatment) with the solution 1.

It is preferable that the removal of the protective layer, the development and the application of the adhesive are performed simultaneously with the solution 1 without performing the pre-washing step. After the development and the coating, it is preferable to remove the remaining developer using a squeegee roller and then dry the developer.

In the developing treatment, the developer may be immersed in the developer 1 time, or may be immersed in the developer 2 or more times. Among them, the method of immersing in the above-mentioned developer 1 or 2 times is preferable.

The immersion may be carried out by drilling the exposed original printing plate into a developer tank containing a developer, or by spraying the developer onto the surface of the exposed original printing plate with a sprayer or the like.

Even when the developing solution is immersed 2 times or more, the same developing solution or a developing solution (fatigue solution) in which the components of the image recording layer are dissolved or dispersed by the developing treatment is immersed 2 times or more, and the process is referred to as a developing treatment (1-solution treatment) with 1-solution.

In the developing treatment, a rubbing member is preferably used, and a rubbing member such as a brush is preferably provided in the developing bath for removing the non-image portion of the image recording layer.

The development treatment can be carried out by a conventional method, preferably at a temperature of 0 to 60 ℃, more preferably at a temperature of 15 to 40 ℃, for example, by dipping the exposure-treated printing original plate in a developer, rubbing it with a brush, or sucking a treatment liquid pumped into an external tank by a pump, spraying it from a sprayer nozzle, rubbing it with a brush, or the like. These development treatments can also be carried out a plurality of times in succession. For example, the treatment can be performed by pumping the treatment liquid injected into an external tank, spraying the treatment liquid from the sprayer nozzle, rubbing the treatment liquid with a brush, and then spraying the treatment liquid from the sprayer nozzle again, rubbing the treatment liquid with a brush. In the case of performing the developing process using an automatic developing processor, it is preferable to recover the processing capability using a replenishing liquid or a fresh developing liquid because the developing liquid is fatigued in accordance with an increase in the processing amount.

In the development process, a glue coater or an automatic development processor known as a PS Plate (Presensitized Plate) or a CTP (Computer to Plate) can be used. When an automatic developing apparatus is used, any of a system in which a developer injected into a developing tank or a developer injected into an external tank is pumped by a pump and sprayed from a sprayer nozzle to perform a process, a system in which a printing plate is immersed and conveyed by an in-liquid guide roller or the like in a tank filled with the developer to perform a process, and a so-called one-shot process system in which a developer that is not substantially used is supplied to each plate in a required amount to perform a process can be applied. In either case, a scrubbing mechanism based on brushes or double-sided pile is more preferred. For example, commercially available automatic development processors (Clean Out Unit C85/C125, Clean-Out Unit + C85/120, FCF 85V, FCF 125V, FCF News (manufactured by Glunz & Jensen), Azura CX85, Azura CX125, and Azura CX150 (manufactured by AGFA GRAPHICS)) can be used, and a device in which a laser exposure section and an automatic development processor are partially integrated can also be used.

Hereinafter, the components of the developing solution used in the developing step and the like will be described in detail.

-pH-

The pH of the developer is preferably 2 to 12, more preferably 5 to 9, and further preferably 7 to 9. From the viewpoint of developability and dispersibility of the image recording layer, it is advantageous to set the pH value high, but with respect to printability, particularly suppression of staining, it is effective to set the pH value low.

Here, the pH was measured at 25 ℃ using a pH meter (model: HM-31, manufactured by DKK-TOA CORPORATION).

Surfactants-

The developer may contain a surfactant such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant.

The developer preferably contains at least one selected from the group consisting of anionic surfactants and amphoteric surfactants, from the viewpoint of brush staining properties.

The developer preferably contains a nonionic surfactant, and more preferably contains at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and an amphoteric surfactant.

Preferred examples of the anionic surfactant include compounds represented by the following formula (I).

R¹-Y¹-X¹ (I)

In the formula (I), R¹Represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group which may have a substituent.

The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.

The cycloalkyl group may be monocyclic or polycyclic. The monocyclic ring is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, and more preferably a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group. Examples of the polycyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a camphyl group, a dicyclopentyl group, an α -sulfoenyl group, and a tricyclodecanyl group.

The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like can be preferably mentioned.

The aryl group is preferably an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4, 6-trimethylphenyl group, a naphthyl group, an anthryl group, a 9, 10-dimethoxyanthryl group and the like.

As the substituent, a monovalent nonmetallic atom group other than a hydrogen atom can be used, and preferable examples thereof include a halogen atom (F, Cl, Br, or I), a hydroxyl group, an alkoxy group, an aryloxy group, an acyl group, an amide group, an ester group, an acyloxy group, a carboxyl group, a carboxylic acid anion group, a sulfonic acid anion group, and the like.

Specific examples of the alkoxy group in the substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentoxy group, a hexoxy group, a dodecoxy group, a stearyloxy group, a methoxyethoxy group, a poly (ethyleneoxy) group, a poly (propyleneoxy) group, and the like, preferably an alkoxy group having 1 to 40 carbon atoms, and more preferably an alkoxy group having 1 to 20 carbon atoms. Examples of the aryloxy group include aryloxy groups having 6 to 18 carbon atoms such as a phenoxy group, a tolyloxy group, a xylyloxy group, a mesityloxy group, a cumene oxy group, a methoxyphenoxy group, an ethoxyphenoxy group, a chlorophenoxy group, a bromophenoxy group, and a naphthyloxy group. Examples of the acyl group include acyl groups having 2 to 24 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, a benzoyl group, and a naphthoyl group. Examples of the amide group include amide groups having 2 to 24 carbon atoms such as an acetamide group, a propionate amide group, a dodecanoic acid amide group, a palmitic acid amide group, a stearic acid amide group, a benzoic acid amide group, and a naphthoic acid amide group. Examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms such as an acetoxy group, a propionyloxy group, a benzoyloxy group, and a naphthoyloxy group. Examples of the ester group include ester groups having 1 to 24 carbon atoms such as a methyl ester group, an ethyl ester group, a propyl ester group, a hexyl ester group, an octyl ester group, a dodecyl ester group, and an octadecyl ester group. The substituent may be composed of a combination of 2 or more of the above substituents.

X¹Represents a sulfonate group, a sulfate monoester group, a carboxylate group or a phosphate group.

Y¹Represents a single bond, -C_nH_2n-、-C_n-mH_2(n-m)OC_mH_2m-、-O-(CH₂CH₂O)_n-、-O-(CH₂CH₂CH₂O)_n-, -CO-NH-or a 2-valent linking group comprising 2 or more combinations thereof, and satisfies n.gtoreq.1 and n.gtoreq.m.gtoreq.0.

Among the compounds represented by the formula (I), compounds represented by the following formula (I-A) or formula (I-B) are preferable from the viewpoint of scratch contamination resistance.

[ chemical formula 6]

In the formulae (I-A) and (I-B), R^A1～R^A10Each independently represents a hydrogen atom or an alkyl group, nA represents an integer of 1 to 3, X^A1And X^A2Each independently represents a sulfonate group, a sulfate monoester group, a carboxylate group or a phosphate group, Y^A1And Y^A2Each independently represents a single bond, -CnH_2n-、-C_n-mH_2(n-m)OC_mH_2m-、-O-(CH₂CH₂O)_n-、-O-(CH₂CH₂CH₂O)_n-, -CO-NH-or a 2-valent linking group comprising 2 or more combinations thereof, and satisfies n.gtoreq.1 and n.gtoreq.m.gtoreq.0, R^A1～R^A5Or R^A6～R^A10Neutralization of Y^A1Or Y^A2The total number of carbon atoms in (2) is 3 or more.

R in the compound represented by the above formula (I-A) or formula (I-B)^A1～R^A5And Y^1AOr, R^A6～R^A10And Y^A2The total carbon number of (2) is preferably 25 or less, more preferably 4 to 20. The structure of the alkyl group may be a straight chain or a branched chain.

X in the compound represented by the formula (I-A) or the formula (I-B)^A1And X^A2Preferably sulfonate or carboxylate groups. And, X^A1And X^A2In the salt structure of The alkali metal salt is particularly preferable because it has good solubility in an aqueous solvent. Among them, sodium salt or potassium salt is particularly preferable.

As the compound represented by the above formula (I-A) or formula (I-B), the description in paragraphs 0019 to 0037 of Japanese patent laid-open No. 2007-206348 can be referred to.

As the anionic surfactant, it is also possible to preferably use the compounds described in paragraphs 0023 to 0028 of Japanese patent application laid-open No. 2006-065321.

The amphoteric surfactant used in the developer is not particularly limited, and examples thereof include amine oxide systems such as alkyldimethylamine oxide, betaine systems such as alkylbetaine, fatty acid amide propylbetaine, and alkylimidazole, and amino acid systems such as sodium alkylaminohydrofate.

In particular, alkyldimethylamine oxides which may have substituents, alkylcarboxybetaines which may have substituents, and alkylsulfobetaines which may have substituents can be preferably used. Specific examples thereof include compounds represented by the formula (2) in paragraph 0256 of jp 2008-203359, compounds represented by the formulae (I), (II) and (VI) in paragraph 0028 of jp 2008-276166, and compounds described in paragraphs 0022 to 0029 of jp 2009-047927.

The zwitterionic surfactant used in the developer is preferably a compound represented by the following formula (1) or a compound represented by the following formula (2).

[ chemical formula 7]

In the formulae (1) and (2), R¹And R¹¹Each independently represents an alkyl group having 8 to 20 carbon atoms or an alkyl group having a linking group having 8 to 20 carbon atoms in total.

R²、R³、R¹²And R¹³Each independently represents a hydrogen atom, an alkyl group or a group having an oxirane structure.

R⁴And R¹⁴Each independently represents a single bond or an alkylene group.

And, R¹、R²、R³And R⁴2 of which may be bonded to each other to form a ring structure, R¹¹、R¹²、R¹³And R¹⁴2 groups in (a) may be bonded to each other to form a ring structure.

In the compound represented by the above formula (1) or the compound represented by the above formula (2), when the total carbon number is increased, the hydrophobic portion is increased, and the solubility of the aqueous system in the developer is lowered. In this case, the solubility is optimized by mixing an organic solvent such as an alcohol which assists dissolution as a dissolution aid in water, but when the total carbon number is excessively increased, the surfactant cannot be dissolved in an appropriate mixing range. Thus, R¹～R⁴Or R¹¹～R¹⁴The total number of carbon atoms of (a) is preferably 10 to 40, more preferably 12 to 30.

From R¹Or R¹¹The alkyl group having a linking group represented represents a structure having a linking group between alkyl groups. That is, when the number of the linker is 1, the linker can be represented by "— alkylene-linker-alkyl". Examples of the linker include an ester bond, a carbonyl bond, and an amide bond. The number of the linker may be 2 or more, but is preferably 1, and particularly preferably an amide bond. The total number of carbon atoms of the alkylene group bonded to the linking group is preferably 1 to 5. The alkylene group may be linear or branched, but is preferably a linear alkylene group. The alkyl group bonded to the linker preferably has 3 to 19 carbon atoms, and may be a straight chain or branched chain, but is preferably a straight chain alkyl group.

At R²Or R¹²In the case of an alkyl group, the number of carbon atoms is preferably 1 to 5, and particularly preferably 1 to 3. May be any 1 of linear chain and branched chain, but is preferably linear chain.

At R³Or R¹³In the case of an alkyl group, the number of carbon atoms is preferably 1 to 5, and particularly preferably 1 to 3. May be any 1 of linear chain and branched chain, but is preferably linear chain.

As a group consisting of R³Or R¹³Containing an oxirane structureCan be exemplified by a group represented by-R^a(CH₂CH₂O)nR^bThe group shown. Wherein R is^aRepresents a single bond, an oxygen atom or a 2-valent organic group (preferably having 10 or less carbon atoms), R^bRepresents a hydrogen atom or an organic group (preferably, a carbon number of 10 or less), and n represents an integer of 1 to 10.

At R⁴And R¹⁴In the case of an alkylene group, the number of carbon atoms is preferably 1 to 5, and particularly preferably 1 to 3. May be any 1 of linear chain and branched chain, but is preferably linear chain.

The compound represented by the formula (1) or the compound represented by the formula (2) preferably has an amide bond as R¹Or R¹¹The linker of (3) more preferably has an amide bond.

Hereinafter, representative examples of the compound represented by the formula (1) or the compound represented by the formula (2) will be described, but the present invention is not limited thereto.

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

The compound represented by the formula (1) or (2) can be synthesized according to a known method. Further, commercially available compounds can also be used. Commercially available compounds represented by the formula (1) include Kawakenkine Chemicals Co., Ltd, SOFTAZ0LINE LPB manufactured by Ltd, SOFTAZ0LINE LPB-R, vistaMAP, TAKEMOTO OIL & FAT Co., Ltd, Takesafu C-157L manufactured by Ltd. Examples of the compound represented by the formula (2) include SoftAZ0LINE LAO manufactured by Kawaken Fine Chemicals Co., Ltd., DAI-ICHI KOGYO SEIYAKU CO., LTD AMOGEN AOL manufactured by LTD.

The zwitterionic surfactant may be used alone in 1 kind or in combination of two or more kinds in the developer.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyrene phenyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, neopentyl glycol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerol fatty acid partial esters, polyoxyethylene glycerin fatty acid partial esters, polyoxyethylene diglycols, fatty acid diethanolamides, N, n-bis-2-hydroxyalkylamines, polyoxyethylenealkylamines, triethanolamine fatty acid esters, trialkylammonium oxides, polyoxyethylenealkylphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, and the like.

In addition, surfactants such as acetylene glycol-based and acetylene alcohol-based ethylene oxide adducts and fluorine-based surfactants can be used in the same manner. These surfactants can be used in combination of two or more.

The nonionic surfactant is preferably a nonionic aromatic ether surfactant represented by the following formula (N1).

X^N-Y^N-O-(A¹)_nB-(A²)_mB-H (N1)

In the formula, X^NRepresents an aromatic group which may have a substituent, Y^NRepresents a single bond or an alkylene group having 1 to 10 carbon atoms, A¹And A²Are mutually different radicals and represent-CH₂CH₂O-or-CH₂CH(CH₃) Any one of O-, nB and mB independently represents an integer of 0 to 100, wherein nB and mB are not 0 at the same time, and nB and mB are not 1 when nB and mB are 0.

In the formula, as X^NExamples of the aromatic group of (2) include a phenyl group, a naphthyl group, and an anthryl group. These aromatic groups may haveAnd (4) a substituent. Examples of the substituent include an organic group having 1 to 100 carbon atoms. In the formula, A and B may be random or block copolymers when both are present.

Specific examples of the organic group having 1 to 100 carbon atoms include saturated or unsaturated, straight or branched aliphatic or aromatic hydrocarbon groups, and examples thereof include alkyl, alkenyl, alkynyl, aryl, aralkyl groups, and other examples include alkoxy, aryloxy, N-alkylamino, N-dialkylamino, N-arylamino, N-diarylamino, N-alkyl-N-arylamino, acyloxy, carbamoyloxy, N-alkylcarbamoyloxy, N-arylcarbamoyloxy, N-dialkylcarbamoyloxy, N-diarylcarbamoyloxy, N-alkyl-N-arylcarbamoyloxy, acylamino, N-alkylamido, N-arylamido, N-arylamido, acyl, alkoxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N-dialkylcarbamoyl, N-arylcarbamoyl, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, the above-mentioned organic group bonded to a polyoxyalkylene chain, polyoxyalkylene chain or the like. The alkyl group may be a straight chain or a branched chain.

Further, as the nonionic surfactant, it is also possible to preferably use the compounds described in paragraphs 0030 to 0040 of Japanese patent application laid-open No. 2006-065321.

The cationic surfactant is not particularly limited, and conventionally known surfactants can be used. For example, alkylamine salts, quaternary ammonium salts, alkylimidazolidium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, and the like can be mentioned.

The surfactant may be used alone in 1 kind, or two or more kinds may be used simultaneously.

The content of the surfactant is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, still more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass, based on the total mass of the developer. When the amount is within the above range, the scratch contamination resistance is further excellent, the dispersibility of the development residue is excellent, and the ink receptivity of the obtained lithographic printing plate is excellent.

Water-soluble high molecular compound-

The developer can contain a water-soluble polymer compound from the viewpoint of adjusting the viscosity of the developer and protecting the plate surface of the obtained lithographic printing plate.

Examples of the water-soluble polymer compound include water-soluble polymer compounds such as soybean polysaccharides, modified starch, gum arabic, dextrin, cellulose derivatives (e.g., carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, etc.) and modified products thereof, pullulan, polyvinyl alcohol and derivatives thereof, polyvinyl pyrrolidone, polyacrylamide and acrylamide copolymers, vinyl methyl ether/maleic anhydride copolymers, vinyl acetate/maleic anhydride copolymers, and styrene/maleic anhydride copolymers.

Conventionally known soybean polysaccharides can be used as the soybean polysaccharides, and for example, Soya fibe (FUJI OIL co., ltd., product) is commercially available, and various grades can be used. The viscosity of a 10 mass% aqueous solution of a substance that can be used is preferably in the range of 10 mPas to 100 mPas.

The modified starch is preferably a starch represented by the following formula (III). As the starch represented by formula (III), any 1 kind of starch of corn, potato, tapioca, rice, wheat, and the like can also be used. The starch can be modified by a method of decomposing the starch with an acid, an enzyme or the like within a range of 5 to 30 glucose residues per 1 molecule, and further adding propylene oxide to an alkali.

[ chemical formula 11]

Wherein the etherification degree (substitution degree) is in the range of 0.05 to 1.2 per glucose unit, n represents an integer of 3 to 30, and m represents an integer of 1 to 3.

Among the water-soluble high molecular compounds, particularly preferred are soybean polysaccharides, modified starch, gum arabic, dextrin, carboxymethyl cellulose, polyvinyl alcohol, and the like.

Two or more kinds of the water-soluble polymer compounds can be used simultaneously.

In the case where the developer contains a water-soluble polymer compound, the content of the water-soluble polymer compound is preferably 3% by mass or less, more preferably 1% by mass or less, relative to the total mass of the developer. In this manner, the viscosity of the developer is appropriate, and accumulation of development residue and the like on the roller member of the automatic development processor can be suppressed.

Other additives

In addition to the above, the developer used in the present invention may contain a wetting agent, an antiseptic agent, a chelate compound, an antifoaming agent, an organic acid, an organic solvent, an inorganic acid, an inorganic salt, and the like.

As the humectant, ethylene glycol, propylene glycol, triethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, diglycerin, and the like can be preferably used. The wetting agent may be used alone or in combination of two or more. The content of the wetting agent is preferably 0.1 to 5% by mass relative to the total mass of the developer.

Examples of the preservative include phenol or a derivative thereof, formalin, an imidazole derivative, sodium dehydroacetate, a 4-isothiazolin-3-one derivative, benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, a benzotriazole derivative, an amidinobuanidine derivative, a quaternary ammonium salt, a derivative such as pyridine, quinoline or guanidine, a diazine, a triazole derivative, oxazole or oxazine derivative, a nitro bromohydrin type 2-bromo-2-nitropropane-1, 3-diol, 1-dibromo-1-nitro-2-ethanol, and 1, 1-dibromo-1-nitro-2-propanol.

The amount of the preservative added is an amount that stably exerts its effect on bacteria, molds, yeasts, and the like, and varies depending on the types of bacteria, molds, and yeasts, but is preferably in the range of 0.01 to 4 mass% with respect to the total mass of the developer. It is also preferable to use two or more preservatives at the same time so as to be effective for various molds and sterilization.

Examples of the chelate compound include ethylenediaminetetraacetic acid, potassium salts thereof, and sodium salts thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetramine hexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediamine triacetic acid, potassium salt thereof, sodium salt thereof; nitrilotriacetic acid, its sodium salt; 1-hydroxyethane-1, 1-diphosphonic acid, potassium salts thereof, sodium salts thereof; and organic phosphonic acids such as aminotri (methylenephosphonic acid), potassium salts thereof, and sodium salts thereof. Instead of the sodium and potassium salts of the chelating agent, organic amine salts are also effective.

The chelating agent is preferably present stably in the composition of the treatment liquid and does not inhibit printability. The content of the chelating agent is preferably 0.001 to 1.0 mass% based on the total mass of the developer.

As the defoaming agent, general silicone-based self-emulsifying type, nonionic type compounds having HLB (Hydrophilic-Lipophilic Balance) of 5 or less, and the like can be used. Silicone-based antifoaming agents are preferred.

In addition, silicone surfactants are considered to be antifoaming agents.

The content of the defoaming agent is preferably in the range of 0.001 to 1.0 mass% with respect to the total mass of the developer.

Examples of the organic acid include citric acid, acetic acid, oxalic acid, malonic acid, salicylic acid, octanoic acid, tartaric acid, malic acid, lactic acid, levulinic acid, p-toluenesulfonic acid, xylenesulfonic acid, phytic acid, and organophosphonic acid. The organic acid may be used in the form of an alkali metal salt or an ammonium salt thereof. The content of the organic acid is preferably 0.01 to 0.5% by mass based on the total mass of the developer.

Examples of the organic solvent include aliphatic hydrocarbons (hexane, heptane, "ISOPAR E, ISOPAR H, ISOPAR G" (Esso Chemical co., ltd), etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, trichloroethylene, monochlorobenzene, etc.), polar solvents, and the like.

Examples of the polar solvent include alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl methanol, n-amyl alcohol, methyl amyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, diethyl phthalate, butyl levulinate, etc.), and others (triethyl phosphate, triethyl ester, triethyl propionate, etc.) Tricresyl phosphate, N-phenylethanolamine, N-phenyldiethanolamine, etc.).

When the organic solvent is insoluble in water, it can be dissolved in water using a surfactant or the like and used, and when the developer contains an organic solvent, the concentration of the solvent in the developer is preferably less than 40% by mass from the viewpoint of safety and flammability.

Examples of the inorganic acid and inorganic salt include phosphoric acid, metaphosphoric acid, monoammonium phosphate, diammonium phosphate, monosodium phosphate, disodium phosphate, monopotassium phosphate, dipotassium phosphate, sodium tripolyphosphate, potassium pyrophosphate, sodium hexametaphosphate, magnesium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, sodium sulfate, potassium sulfate, ammonium sulfate, sodium sulfite, ammonium sulfite, sodium hydrogensulfate, and nickel sulfate. The content of the inorganic salt is preferably 0.01 to 0.5 mass% with respect to the total mass of the developer.

The developer can be prepared by dissolving or dispersing the above-mentioned respective components in water as required. The solid content concentration of the developer is preferably 2 to 25% by mass. As the developer, a concentrated solution can be prepared and used by diluting with water at the time of use.

The developer is preferably an aqueous developer.

The developer preferably contains an alcohol compound from the viewpoint of dispersibility of the development residue.

Examples of the alcohol compound include methanol, ethanol, propanol, isopropanol, and benzyl alcohol. Among them, benzyl alcohol is preferable.

From the viewpoint of dispersibility of the developing residue, the content of the alcohol compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass, based on the total mass of the developer.

< printing Process >

The printing method using the printing plate obtained by the developer treatment method is not particularly limited, and printing can be performed by a known method.

For example, a method of supplying ink and, if necessary, dampening solution to a printing plate and printing is performed.

The printing method according to the present invention may include other known steps in addition to the above-described steps. Examples of the other steps include a plate checking step of checking the position, orientation, and the like of the original printing plate before each step, and a checking step of checking the printed image after the developing step.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, "%" and "part(s)" mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified. In the polymer compound, the molecular weight is a mass average molecular weight (Mw) and the ratio of the structural repeating units is a mole percentage unless otherwise specified. The mass average molecular weight (Mw) is a value measured as a polystyrene equivalent value by a Gel Permeation Chromatography (GPC) method.

[ examples 1 to 38 and comparative examples 1 to 4 ]

< production of support 1 >

The following treatments (a) to (f) were performed on an aluminum plate (material JIS a 1052) having a thickness of 0.3mm to produce the support 1. Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(a) Alkali etching treatment

Blowing from the injection pipe to the aluminum plateAn aqueous solution having a sodium concentration of 25% by mass, an aluminum ion concentration of 100g/L and a temperature of 60 ℃ was subjected to etching treatment. The etching amount of the surface subjected to the electrochemical roughening treatment after the aluminum plate was 3g/m²。

(b) Decontamination treatment

An aqueous solution of sulfuric acid (concentration: 300g/L) having a temperature of 35 ℃ was sprayed from the spray pipe for 5 seconds to perform a desmutting treatment.

(c) Electrolytic graining treatment

Electrochemical roughening treatment was continuously performed using a flat cell type electrolytic cell using an alternating current power supply of 60Hz and an electrolytic solution (liquid temperature 35 ℃) in which aluminum chloride was dissolved in a 1 mass% hydrochloric acid aqueous solution to set the aluminum ion concentration at 4.5 g/L. The waveform of the ac power source uses a sine wave. In the electrochemical roughening treatment, the current density at the time of anode reaction of the aluminum plate at the peak of the alternating current was 30A/dm². The ratio of the sum of the currents at the anodic reaction to the sum of the currents at the cathodic reaction of the aluminum plate was 0.95. The electric quantity is 480C/dm calculated by the total current at the anode of the aluminum plate ². The electrolyte solution is stirred in the electrolytic cell by circulating the solution using a pump.

(d) Alkali etching treatment

An aqueous solution having a caustic soda concentration of 5% by mass, an aluminum ion concentration of 5g/L and a temperature of 35 ℃ was sprayed from an injection tube onto an aluminum plate to perform etching treatment. The surface of the aluminum plate subjected to the electrolytic roughening treatment was etched in an amount of 0.05g/m²。

(e) Decontamination treatment

An aqueous solution having a sulfuric acid concentration of 300g/L, an aluminum ion concentration of 5g/L and a liquid temperature of 35 ℃ was blown from the injection pipe for 5 seconds to perform a desmutting treatment.

(f) Anodic oxidation treatment

For the aluminum plate, a 22 mass% phosphoric acid aqueous solution was used as an electrolyte, and the solution temperature was 38 ℃ and the current density was 15A/dm²The anodic oxidation treatment was performed under the conditions of (1). Then, water washing was performed using a nebulizer. The amount of the oxide film was 1.5g/m². The average diameter of micropores on the printing-side surface of the support 1 was 30 nm.

Printing surface side of aluminum supportThe average diameter of micropores on the surface is determined by the following method. The surface on the side of the aluminum support on the printing surface was observed with an FE-SEM at a magnification of 15 ten thousand times, and the surface was measured to be present at 400X 600nm in 4 images obtained²The diameter (diameter) of the micropores in the range of (1), and an average value is calculated. In the case where the shape of the micropores is not circular, a circle-equivalent diameter is used. The "equivalent circle diameter" refers to a diameter of a circle when the shape of the opening is assumed to be a circle having a projection area equal to the projection area of the opening.

< production of support 2 to support 4 >

The following treatments (A-a) to (A-g) were applied to aluminum sheets (aluminum alloy sheets) of material 1S having a thickness of 0.3mm to produce supports 2 to 4. Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(A-a) alkaline etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 5g/m²。

(A-b) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 150g/L was sprayed as an acidic aqueous solution onto an aluminum plate for 3 seconds by a sprayer, and a desmutting treatment was performed.

(A-c) electrochemical roughening treatment Using hydrochloric acid aqueous solution

An electrolytic solution having a hydrochloric acid concentration of 14g/L, an aluminum ion concentration of 13g/L and a sulfuric acid concentration of 3g/L was used, and electrochemical roughening treatment was performed by an alternating current. The liquid temperature of the electrolyte was 30 ℃. The aluminum ion concentration was adjusted by adding aluminum chloride.

The AC current has a sine wave with symmetrical positive and negative waveforms, a frequency of 50Hz, an anode reaction time and a cathode reaction time of 1 cycle of the AC current of 1:1, and a current density of 75A/dm (peak current value) of the AC current waveform ². And the electric quantity is exposed to the sun by the aluminum plateThe total amount of electricity supplied by the polar reaction is 450C/dm²Electrolytic treatment at a rate of per 112.5C/dm²The energization was performed 4 times at intervals of 4 seconds. A carbon electrode was used as a counter electrode of the aluminum plate.

(A-d) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% onto an aluminum plate at a temperature of 45 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 0.2g/m²。

(A-e) decontamination treatment Using acidic aqueous solution

The waste liquid (aqueous solution having a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5 g/L) generated in the anodizing treatment step at a liquid temperature of 30 ℃ was sprayed as an acidic aqueous solution to the aluminum plate by a sprayer for 3 seconds, and the aluminum plate was subjected to desmutting treatment.

(A-f) anodic oxidation treatment

The anodic oxidation treatment was performed using an anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 30A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 0.3g/m²The anodic oxide coating of (1).

In the anodizing apparatus 410 shown in FIG. 3, an aluminum plate 416 is conveyed as indicated by an arrow in FIG. 3. In the power supply tank 412 storing the electrolyte 418, the aluminum plate 416 is charged (+) by the power supply electrode 420. The aluminum plate 416 is conveyed upward by the roller 422 in the power supply tank 412, is changed in direction downward by the rolling roller 424, is conveyed toward the electrolytic treatment tank 414 in which the electrolytic solution 426 is stored, and is changed in direction horizontally by the roller 428. Subsequently, the aluminum plate 416 is charged (-) by the electrolysis electrode 430, and thereby an anodic oxide film is formed on the surface thereof, and the aluminum plate 416 separated from the electrolytic treatment tank 414 is conveyed to the subsequent step. In the anodizing apparatus 410, the direction changing mechanism is constituted by the rollers 422, the rolling rollers 424, and the rollers 428, and the aluminum sheet 416 is conveyed in the mountain-like shape and the inverted U-like shape by the rollers 422, 424, and 428 between the feeding bath 412 and the electrolytic treatment bath 414. The feeding electrode 420 and the electrolysis electrode 430 are connected to a dc power source 434.

(A-g) hole enlarging treatment

The anodized aluminum plate was immersed in a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at 28 ℃ for 3 seconds (support 2), at 40 ℃ for 3 seconds (support 3), and at 40 ℃ for 15 seconds (support 4) to expand the pores. Then, water washing was performed using a nebulizer. The average diameters of micropores on the printing surface side surfaces of the support 2, the support 3, and the support 4 were 13nm, 30nm, and 100nm, respectively.

< production of support body 5 >

The support 5 was produced by subjecting an aluminum plate (aluminum alloy plate) of 1S, which was 0.3mm thick, to the following treatments (B-a) to (B-h). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(B-a) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 5g/m²。

(B-B) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 150g/L was sprayed as an acidic aqueous solution onto an aluminum plate for 3 seconds by a sprayer, and a desmutting treatment was performed.

(B-c) electrochemical roughening treatment Using hydrochloric acid aqueous solution

An electrolytic solution having a hydrochloric acid concentration of 14g/L, an aluminum ion concentration of 13g/L and a sulfuric acid concentration of 3g/L was used, and electrochemical roughening treatment was performed by an alternating current. The liquid temperature of the electrolyte was 30 ℃. The aluminum ion concentration was adjusted by adding aluminum chloride.

The waveform of the alternating current is a sine wave with symmetrical positive and negative waveforms, the frequency is 50Hz, the anode reaction time and the cathode reaction time in 1 period of the alternating current are 1:1, and the current density is 7 in terms of the peak current value of the alternating current waveform5A/dm². The total amount of electricity supplied to the anode reaction from the aluminum plate was 450C/dm²Electrolytic treatment at a rate of per 112.5C/dm²The energization was performed 4 times at intervals of 4 seconds. A carbon electrode was used as a counter electrode of the aluminum plate.

(B-d) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% onto an aluminum plate at a temperature of 45 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 0.2g/m²。

(B-e) decontamination treatment Using acidic aqueous solution

The waste liquid (aqueous solution having a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5 g/L) generated in the anodizing treatment step at a liquid temperature of 30 ℃ was sprayed as an acidic aqueous solution to the aluminum plate by a sprayer for 3 seconds, and the aluminum plate was subjected to desmutting treatment.

(B-f) anodizing treatment in stage 1

The anodic oxidation treatment of stage 1 was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 30A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 0.3g/m²The anodic oxide coating of (1).

(B-g) hole enlarging treatment

The anodized aluminum plate was immersed in a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at 40 ℃ for 3 seconds to perform a hole expanding treatment.

(B-h) anodic Oxidation treatment at stage 2

The anodic oxidation treatment of the 2 nd stage was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 13A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.1g/m²The anodic oxide coating of (1). Then, water washing was performed using a nebulizer. Of micro-holes on the printing surface side surface of the support body 5The average diameter was 30 nm.

< production of support body 6 >

The support 6 was produced by subjecting an aluminum plate (aluminum alloy plate) of 1S, which was 0.3mm thick, to the following treatments (D-a) to (D-l). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(D-a) mechanical roughening treatment (brushing method)

Using an apparatus having the structure shown in FIG. 5, a pumice powder suspension (specific gravity 1.1 g/cm)³) The aluminum plate surface was subjected to mechanical roughening treatment by a rotating bristle brush while being supplied as a polishing slurry. In fig. 5, 1 is an aluminum plate, 2 and 4 are roller brushes (bristle brush in this embodiment), 3 is a grinding slurry, and 5, 6, 7 and 8 are backup rollers.

In the mechanical roughening treatment, the median particle diameter (μm) of the abrasive was set to 30 μm, the number of brushes was set to 4, and the brush rotation speed (rpm) was set to 250 rpm. The bristle brush is made of 6.10 nylon, and has a diameter of 0.3mm and a length of 50 mm. The brush was made dense by drilling holes in a 300mm diameter stainless steel cylinder and tufting. The distance between 2 support rollers (200 mm) below the bristle tuft brush was 300 mm. The tuft brush was pressed until the load of the drive motor rotating the brush was 10kW greater than the load before pressing the tuft brush against the aluminum plate. The direction of rotation of the brush is the same as the direction of movement of the aluminum plate.

(D-b) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 10g/m ²。

(D-c) decontamination treatment Using acidic aqueous solution

A waste solution of nitric acid used in the next step of electrochemical graining treatment of an aluminum plate was sprayed with a liquid temperature of 35 ℃ for 3 seconds by a sprayer as an acidic aqueous solution, and desmutting treatment was performed.

(D-D) electrochemical roughening treatment Using nitric acid aqueous solution

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. As the electrolyte, an electrolyte having an aluminum ion concentration of 4.5g/L and a liquid temperature of 35 ℃ was used by adding aluminum nitrate to an aqueous solution of 10.4g/L nitric acid. The ac power waveform was the waveform shown in fig. 1, and the carbon electrode was subjected to electrochemical roughening treatment using a trapezoidal rectangular wave ac with a time tp until the current value reached the peak from zero of 0.8msec and a duty ratio of 1:1 as the counter electrode. Ferrite is used for the auxiliary anode. The electrolytic cell used was one having the structure shown in FIG. 2. The current density was 30A/dm as the peak value of the current²5% of the current from the power supply is shunted to the auxiliary anode. Electric quantity (C/dm)²) The sum of the electric quantity when the aluminum plate is taken as the anode is 185C/dm²。

(D-e) alkali etching treatment

An aluminum plate was etched by spraying an aqueous solution of caustic soda having a caustic soda concentration of 27 mass% and an aluminum ion concentration of 2.5 mass% at a temperature of 50 ℃ with a sprayer. The amount of aluminum dissolved was 0.5g/m ²。

(D-f) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution onto an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(D-g) electrochemical roughening treatment Using hydrochloric acid aqueous solution

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. As the electrolyte, an electrolyte having an aluminum ion concentration adjusted to 4.5g/L at a liquid temperature of 35 ℃ was used by adding aluminum chloride to an aqueous solution of 6.2g/L hydrochloric acid. The ac power waveform was the waveform shown in fig. 1, and the carbon electrode was subjected to electrochemical roughening treatment using a trapezoidal rectangular wave ac with a time tp until the current value reached the peak from zero of 0.8msec and a duty ratio of 1:1 as the counter electrode. Ferrite is used for the auxiliary anode. The electrolytic cell used was one having the structure shown in FIG. 2. The current density is 25A/dm in terms of peak value of current²Electric quantity (C/dm) in hydrochloric acid electrolysis²) Sum of electric quantity when aluminum plate is used as anodeIs counted as 63C/dm²。

(D-h) alkali etching treatment

An aluminum plate was etched by spraying an aqueous solution of caustic soda having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at a temperature of 60 ℃ with a sprayer. The amount of aluminum dissolved was 0.1g/m ²。

(D-i) decontamination treatment Using acidic aqueous solution

The waste liquid (aqueous solution having a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5 g/L) generated in the anodizing treatment step at a liquid temperature of 35 ℃ was sprayed as an acidic aqueous solution onto an aluminum plate for 4 seconds by a sprayer, and the aluminum plate was subjected to desmutting treatment.

(D-j) anodic oxidation treatment

The anodic oxidation treatment was performed using an anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 30A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.4g/m²The anodic oxide coating of (1).

(D-k) hole enlarging treatment

The anodized aluminum plate was immersed in a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at a temperature of 40 ℃ for 3 seconds to perform a hole expanding treatment. The average diameter of micropores on the printing-side surface of the aluminum support was 30 nm.

(D-l) hydrophilization treatment

In order to ensure the hydrophilicity of the non-image portion, the aluminum plate was immersed in a 2.5 mass% aqueous solution of sodium silicate No. 3 at 50 ℃ for 7 seconds to carry out silicate treatment. The amount of Si deposited was 8.5mg/m². Then, water washing was performed using a nebulizer.

< production of support body 7 >

The support 7 was produced by subjecting an aluminum plate (aluminum alloy plate) of 1S, which was 0.3mm thick, to the following treatments (F-a) to (F-g). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(F-a) alkaline etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 5g/m²。

(F-b) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 150g/L was sprayed as an acidic aqueous solution onto an aluminum plate for 3 seconds by a sprayer, and a desmutting treatment was performed.

(F-c) electrochemical roughening treatment

An electrolytic solution having a hydrochloric acid concentration of 14g/L, an aluminum ion concentration of 13g/L and a sulfuric acid concentration of 3g/L was used, and electrochemical roughening treatment was performed by an alternating current. The liquid temperature of the electrolyte was 30 ℃. The aluminum ion concentration was adjusted by adding aluminum chloride.

The AC current has a sine wave with symmetrical positive and negative waveforms, a frequency of 50Hz, an anode reaction time and a cathode reaction time of 1 cycle of the AC current of 1:1, and a current density of 75A/dm (peak current value) of the AC current waveform ². The total amount of electricity supplied to the anode reaction from the aluminum plate was 450C/dm²Electrolytic treatment at a rate of per 112.5C/dm²The energization was performed 4 times at intervals of 4 seconds. A carbon electrode was used as a counter electrode of the aluminum plate.

(F-d) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% onto an aluminum plate at a temperature of 45 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 0.2g/m²。

(F-e) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 35 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution to an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(F-F) anodizing treatment in stage 1

Using a method based on that shown in FIG. 3The anodic oxidation apparatus for direct current electrolysis having the structure performs the anodic oxidation treatment of the 1 st stage. 150g/L phosphoric acid aqueous solution is used as electrolyte, and the current density is 4.5A/dm at the liquid temperature of 35 DEG C²The anodic oxidation treatment was carried out under the conditions of (1) g/m of the amount of the formed coating film²The anodic oxide coating of (1).

(F-g) anodic Oxidation treatment of stage 2

The anodic oxidation treatment of the 2 nd stage was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 13A/dm ²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.1g/m²The anodic oxide coating of (1). Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 7 was 40 nm.

< production of support body 8 >

The support 8 was produced by subjecting an aluminum plate (aluminum alloy plate) of 1S, which was 0.3mm thick, to the following treatments (G-a) to (G-h). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(G-a) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 5g/m²。

(G-b) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 150g/L was sprayed as an acidic aqueous solution onto an aluminum plate for 3 seconds by a sprayer, and a desmutting treatment was performed.

(G-c) electrochemical roughening treatment

An electrolytic solution having a hydrochloric acid concentration of 14g/L, an aluminum ion concentration of 13g/L and a sulfuric acid concentration of 3g/L was used, and electrochemical roughening treatment was performed by an alternating current. The liquid temperature of the electrolyte was 30 ℃. The aluminum ion concentration was adjusted by adding aluminum chloride.

The AC current has a sine wave with symmetrical positive and negative waveforms, a frequency of 50Hz, an anode reaction time and a cathode reaction time of 1 cycle of the AC current of 1:1, and a current density of 75A/dm (peak current value) of the AC current waveform². The total amount of electricity supplied to the anode reaction from the aluminum plate was 450C/dm²Electrolytic treatment at a rate of per 112.5C/dm²The energization was performed 4 times at intervals of 4 seconds. A carbon electrode was used as a counter electrode of the aluminum plate.

(G-d) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% onto an aluminum plate at a temperature of 45 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 0.2g/m²。

(G-e) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 35 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution to an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(G-f) anodizing treatment in stage 1

The anodic oxidation treatment of stage 1 was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. 150g/L phosphoric acid aqueous solution is used as electrolyte, and the current density is 4.5A/dm at the liquid temperature of 35 DEG C ²The anodic oxidation treatment was carried out under the conditions of (1) g/m of the amount of the formed coating film²The anodic oxide coating of (1).

(G-G) hole enlarging treatment

The anodized aluminum plate was immersed in a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at a temperature of 40 ℃ for 4 seconds to perform a hole expanding treatment.

(G-h) anodic Oxidation treatment of stage 2

The anodic oxidation treatment of the 2 nd stage was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 13A/dm²Under the conditions ofThe film amount was 2.1g/m by the extreme oxidation treatment²The anodic oxide coating of (1). Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 8 was 100 nm.

< production of support 9 >

The support 9 was produced by subjecting an aluminum plate (aluminum alloy plate) of material 1S having a thickness of 0.3mm to the following treatments (H-a) to (H-g). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(H-a) alkaline etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 5g/m ²。

(H-b) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 150g/L was sprayed as an acidic aqueous solution onto an aluminum plate for 3 seconds by a sprayer, and a desmutting treatment was performed.

(H-c) electrochemical roughening treatment

An electrolytic solution having a hydrochloric acid concentration of 14g/L, an aluminum ion concentration of 13g/L and a sulfuric acid concentration of 3g/L was used, and electrochemical roughening treatment was performed by an alternating current. The liquid temperature of the electrolyte was 30 ℃. The aluminum ion concentration was adjusted by adding aluminum chloride.

The AC current has a sine wave with symmetrical positive and negative waveforms, a frequency of 50Hz, an anode reaction time and a cathode reaction time of 1 cycle of the AC current of 1:1, and a current density of 75A/dm (peak current value) of the AC current waveform². The total amount of electricity supplied to the anode reaction from the aluminum plate was 450C/dm²Electrolytic treatment at a rate of per 112.5C/dm²The energization was performed 4 times at intervals of 4 seconds. A carbon electrode was used as a counter electrode of the aluminum plate.

(H-d) alkali etching treatment

Spraying 5 mass of caustic soda with a sprayer at 45 ℃ onto an aluminum plate% and aluminum ion concentration 0.5 mass% was etched with an aqueous solution of caustic soda. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 0.2g/m ²。

(H-e) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 35 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution to an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(H-f) anodizing treatment in stage 1

The anodic oxidation treatment of stage 1 was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. 150g/L phosphoric acid aqueous solution is used as electrolyte, and the current density is 4.5A/dm at the liquid temperature of 35 DEG C²The anodic oxidation treatment was carried out under the conditions of (1) g/m of the amount of the formed coating film²The anodic oxide coating of (1).

(H-g) stage 2 anodizing treatment

150g/L phosphoric acid aqueous solution is used as electrolyte, and the current density is 4.5A/dm at the liquid temperature of 35 DEG C²The anodic oxidation treatment was carried out under the conditions of (1.2 g/m) of the amount of the formed coating film²The anodic oxide coating of (1). Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 9 was 40 nm.

< production of support body 10 >

The support 10 was produced by subjecting an aluminum plate (aluminum alloy plate) of 1S, which was 0.3mm thick, to the following treatments (I-a) to (I-h). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(I-a) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 5g/m²。

(I-b) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 150g/L was sprayed as an acidic aqueous solution onto an aluminum plate for 3 seconds by a sprayer, and a desmutting treatment was performed.

(I-c) electrochemical roughening treatment

An electrolytic solution having a hydrochloric acid concentration of 14g/L, an aluminum ion concentration of 13g/L and a sulfuric acid concentration of 3g/L was used, and electrochemical roughening treatment was performed by an alternating current. The liquid temperature of the electrolyte was 30 ℃. The aluminum ion concentration was adjusted by adding aluminum chloride.

The AC current has a sine wave with symmetrical positive and negative waveforms, a frequency of 50Hz, an anode reaction time and a cathode reaction time of 1 cycle of the AC current of 1:1, and a current density of 75A/dm (peak current value) of the AC current waveform². The total amount of electricity supplied to the anode reaction from the aluminum plate was 450C/dm²Electrolytic treatment at a rate of per 112.5C/dm²The energization was performed 4 times at intervals of 4 seconds. A carbon electrode was used as a counter electrode of the aluminum plate.

(I-d) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% onto an aluminum plate at a temperature of 45 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 0.2g/m²。

(I-e) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 35 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution to an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(I-f) stage 1 anodizing treatment

The anodic oxidation treatment of stage 1 was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. 150g/L phosphoric acid aqueous solution is used as electrolyte, and the current density is 4.5A/dm at the liquid temperature of 35 DEG C²The anodic oxidation treatment was carried out under the conditions of (1) g/m of the amount of the formed coating film²The anodic oxide coating of (1).

(I-g) hole enlarging treatment

The aluminum plate subjected to the anodic oxidation treatment was immersed in a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at a temperature of 40 ℃ for 8 seconds to perform a hole expanding treatment.

(I-h) stage 2 anodic Oxidation treatment

The anodic oxidation treatment of the 2 nd stage was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. 150g/L phosphoric acid aqueous solution is used as electrolyte, and the current density is 4.5A/dm at the liquid temperature of 35 DEG C ²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.1g/m²The anodic oxide coating of (1). Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 10 was 148 nm.

< production of support 11 >

The support 11 was fabricated by subjecting an aluminum plate (aluminum alloy plate) of 1S material having a thickness of 0.3mm to the following treatments (A-a) to (A-g). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(A-a) alkaline etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 5g/m²。

(A-b) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 150g/L was sprayed as an acidic aqueous solution onto an aluminum plate for 3 seconds by a sprayer, and a desmutting treatment was performed.

(A-c) electrochemical roughening treatment Using hydrochloric acid aqueous solution

An electrolytic solution having a hydrochloric acid concentration of 14g/L, an aluminum ion concentration of 13g/L and a sulfuric acid concentration of 3g/L was used, and electrochemical roughening treatment was performed by an alternating current. The liquid temperature of the electrolyte was 30 ℃. The aluminum ion concentration was adjusted by adding aluminum chloride.

The waveform of the alternating current is a sine wave with symmetrical positive and negative waveforms, the frequency is 50Hz, and the alternating current in 1 periodThe anode reaction time and the cathode reaction time are 1:1, and the current density is 75A/dm calculated by the peak current value of an alternating current waveform². The total amount of electricity supplied to the anode reaction from the aluminum plate was 450C/dm²Electrolytic treatment at a rate of per 112.5C/dm²The energization was performed 4 times at intervals of 4 seconds. A carbon electrode was used as a counter electrode of the aluminum plate.

(A-d) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% onto an aluminum plate at a temperature of 45 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 0.2g/m²。

(A-e) decontamination treatment Using acidic aqueous solution

The waste liquid (aqueous solution having a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5 g/L) generated in the anodizing treatment step at a liquid temperature of 30 ℃ was sprayed as an acidic aqueous solution to the aluminum plate by a sprayer for 3 seconds, and the aluminum plate was subjected to desmutting treatment.

(A-f) anodic oxidation treatment

The anodic oxidation treatment was performed using an anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 30A/dm ²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.4g/m²The anodic oxide coating of (1).

In the anodizing apparatus 410 shown in FIG. 3, an aluminum plate 416 is conveyed as indicated by an arrow in FIG. 3. In the power supply tank 412 storing the electrolyte 418, the aluminum plate 416 is charged (+) by the power supply electrode 420. The aluminum plate 416 is conveyed upward by the roller 422 in the power supply tank 412, is changed in direction downward by the rolling roller 424, is conveyed toward the electrolytic treatment tank 414 in which the electrolytic solution 426 is stored, and is changed in direction horizontally by the roller 428. Subsequently, the aluminum plate 416 is charged (-) by the electrolysis electrode 430, and thereby an anodic oxide film is formed on the surface thereof, and the aluminum plate 416 separated from the electrolytic treatment tank 414 is conveyed to the subsequent step. In the anodizing apparatus 410, the direction changing mechanism is constituted by the rollers 422, the rolling rollers 424, and the rollers 428, and the aluminum sheet 416 is conveyed in the mountain-like shape and the inverted U-like shape by the rollers 422, 424, and 428 between the feeding bath 412 and the electrolytic treatment bath 414. The feeding electrode 420 and the electrolysis electrode 430 are connected to a dc power source 434.

(A-g) hole enlarging treatment

The anodized aluminum plate was immersed in a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at 40 ℃ for 3 seconds to perform a hole expanding treatment. Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 11 was 30 nm.

< production of support body 12 >

The following treatments (a) to (m) were performed on an aluminum alloy sheet having a thickness of 0.3mm and a composition shown in table 1, to produce a support body 12. Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

[ Table 1]

a) Mechanical roughening (grain brushing method)

Suspending the pumice powder in a suspension (specific gravity 1.1 g/cm)³) The aluminum plate surface was subjected to mechanical roughening treatment by a rotating bristle brush while being supplied as a polishing slurry.

In the mechanical roughening treatment, the median particle diameter of the pumice powder of the abrasive was 30 μm, the number of bristle brush was 4, and the rotational speed of the bristle brush was 250 rpm. The bristle brush is made of 6.10 nylon, and has a diameter of 0.3mm and a length of 50 mm. The bristle brush is a brush made dense by drilling a hole in a stainless steel cylinder having a diameter of 300mm and implanting bristles. The distance between 2 support rollers (200 mm) below the bristle tuft brush was 300 mm. The tuft brush was pressed until the load of the drive motor rotating the brush was 10kW greater than the load before pressing the tuft brush against the aluminum plate. The rotating direction of the bristle tuft brush is the same as the moving direction of the aluminum plate.

(b) Alkali etching treatment

An aluminum plate was etched by blowing a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% through a jet pipe at a temperature of 70 ℃. The aluminum dissolution amount was 10g/m²。

(c) Decontamination in acidic aqueous solutions

The decontamination treatment was performed in an aqueous nitric acid solution. The nitric acid aqueous solution used for the desmear treatment was a nitric acid electrolytic solution used for the electrochemical roughening in the next step. The liquid temperature was 35 ℃. The desmutting treatment was performed for 3 seconds by spraying a desmutting liquid using a sprayer.

(d) Electrochemical roughening treatment

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. As the electrolyte, an electrolyte prepared by adding aluminum nitrate to an aqueous solution having a temperature of 35 ℃ and a nitric acid concentration of 10.4g/L to adjust the aluminum ion concentration to 4.5g/L was used. The AC power waveform was subjected to electrochemical roughening treatment using a trapezoidal rectangular AC current with a current value of 0.8msec and a duty ratio of 1:1 as the time tp until the current value reached the peak from zero, and using a carbon electrode as the counter electrode. Ferrite is used for the auxiliary anode. The current density was 30A/dm as the peak value of the current²5% of the current from the power supply is shunted to the auxiliary anode. The total electric quantity is 185C/dm ²。

(e) Alkali etching treatment

An aluminum plate was etched by blowing a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% through a jet pipe at a temperature of 50 ℃. The amount of aluminum dissolved was 0.5g/m²。

(f) Decontamination in acidic aqueous solutions

An aqueous sulfuric acid solution having a liquid temperature of 60 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution to an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(g) Electrochemical roughening treatment

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. Electrolyte solutionAn electrolytic solution was used in which aluminum salt was added to an aqueous solution having a solution temperature of 35 ℃ and a hydrochloric acid concentration of 6.2g/L to adjust the aluminum ion concentration to 4.5 g/L. The AC power waveform was subjected to electrochemical roughening treatment using a trapezoidal rectangular wave AC with a current value of 0.8msec and a duty ratio of 1:1 as tp from zero to the peak, and using a carbon electrode as the counter electrode. Ferrite is used for the auxiliary anode. The current density is 25A/dm in terms of peak value of current²The electric quantity in hydrochloric acid electrolysis is 63C/dm based on the sum of the electric quantities when the aluminum plate is used as the anode²。

(h) Alkali etching treatment

An aluminum plate was etched by blowing a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% through a jet pipe at a temperature of 50 ℃. The amount of aluminum dissolved was 0.1g/m ²。

(i) Decontamination in acidic aqueous solutions

An aqueous sulfuric acid solution (containing 5g/L of aluminum ions in an aqueous solution of 170g/L of sulfuric acid) used in the anodizing treatment step at a liquid temperature of 35 ℃ was sprayed as an acidic aqueous solution onto an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(j) 1 st anodic oxidation treatment

The anodic oxidation treatment of stage 1 was performed using an anodic oxidation apparatus based on direct current electrolysis. An anodic oxide film having a predetermined film thickness was formed by performing the anodic oxidation treatment under the conditions shown in table 2. An aqueous solution containing the components shown in table 2 was used as the electrolyte. In tables 2 to 4, "component concentration" indicates the content concentration (g/L) of each component described in the column of "solution component".

[ Table 2]

(k) 2 nd anodic oxidation treatment

The anodic oxidation treatment of the 2 nd stage was performed using an anodic oxidation apparatus based on direct current electrolysis. An anodic oxide film having a predetermined film thickness was formed by performing the anodic oxidation treatment under the conditions shown in table 3. An aqueous solution containing the components shown in table 3 was used as the electrolyte.

[ Table 3]

(l) 3 rd anodizing treatment

The anodic oxidation treatment of the 3 rd stage was performed using an anodic oxidation apparatus based on direct current electrolysis. An anodic oxide film having a predetermined film thickness was formed by performing the anodic oxidation treatment under the conditions shown in table 4. An aqueous solution containing the components shown in table 4 was used as the electrolyte.

[ Table 4]

(m) hydrophilization treatment

In order to ensure the hydrophilicity of the non-image area, the silicate treatment was performed by immersing the non-image area in a 2.5 mass% aqueous solution of sodium silicate No. 3 at 50 ℃ for 7 seconds. Then, water washing was performed using a nebulizer. The amount of Si deposited was 8.5mg/m²。

The average diameter (surface layer average diameter) of the surface of the anodic oxide film of the large-diameter hole portion in the obtained anodic oxide film having micropores, the average diameter (bottom portion average diameter) of the communication position of the large-diameter hole portion, the average diameter (small-diameter hole portion diameter) of the communication position of the small-diameter hole portion, the average depths of the large-diameter hole portion and the small-diameter hole portion, the thickness (barrier layer thickness) of the anodic oxide film from the bottom portion of the small-diameter hole portion to the surface of the aluminum plate, the density of the small-diameter hole portion, and the like are shown in tables 5 and 6. The small-diameter hole portion includes a 1 st small-diameter hole portion and a 2 nd small-diameter hole portion having different depths, and the deeper one is referred to as a 1 st small-diameter hole portion.

[ Table 5]

[ Table 6]

In table 6, the average value and the minimum value are shown as the barrier layer thickness. The average values are as follows: the thickness of the anodic oxide film from the bottom of the 1 st small-diameter hole portion to the surface of the aluminum plate was measured at 50 points, and the values were arithmetically averaged.

The average diameter of the micropores (average diameter of the large-diameter hole portion and the small-diameter hole portion) was as follows: the surface of the large-diameter hole and the surface of the small-diameter hole were observed in 4 pieces of N with a field emission scanning electron microscope (FE-SEM) having a magnification of 15 ten thousand, and the presence of N in 400 × 600nm in the obtained 4 images was measured²The diameters of the micropores (large diameter hole portions and small diameter hole portions) in the range of (1) are averaged. In addition, when the depth of the large-diameter hole portion is deep and it is difficult to measure the diameter of the small-diameter hole portion, the upper portion of the anodic oxide film is cut, and then various diameters are obtained.

The average depth of the large-diameter pores was a value obtained by observing a cross section of the support (anodic oxide film) with FE-TEM at a magnification of 50 ten thousand times, measuring the distance from the surface of 60 (N: 60) arbitrary micropores to the communication position in the obtained image, and averaging them. The average depth of the small-diameter pores is a value obtained by observing the cross section of the support (anodic oxide film) by FE-SEM (5 ten thousand times), measuring the depth of any 25 micropores in the obtained image, and averaging the measured depths.

The "communicating portion density" is the density of the small-diameter holes in the cross section of the anodic oxide film at the communicating position, and the "surface area increase rate" is a value calculated from the following formula (a).

Formula (A)

Surface area increase rate of 1+ pore density × ((pi × (average diameter of surface layer/2 + average diameter of bottom part/2) × ((average diameter of bottom part/2-average diameter of surface layer/2)²+ depth A²)^1/2+ π X (bottom average diameter/2)²-pi x (surface layer flat)Average diameter/2)²))

In the column of "average depth (nm)" of the small-diameter hole portions, the average depth of the 2 nd small-diameter hole portion is shown on the left side, and the average depth of the 1 st small-diameter hole portion is shown on the right side. In the column of "communicating portion density" of the small-diameter hole portion, the density of the 1 st small-diameter hole portion and the communicating portion density of the small-diameter hole portion are shown in parentheses.

The average diameter of the 1 st small-diameter hole portion located from the bottom of the 2 nd small-diameter hole portion to the bottom of the 1 st small-diameter hole portion was 12 nm.

< production of support body 13 >

The support body 13 was produced by subjecting an aluminum plate (aluminum alloy plate) of 1S material having a thickness of 0.3mm to the following treatments (J-a) to (J-m). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(J-a) mechanical roughening treatment (brushing method)

Using an apparatus having the structure shown in FIG. 5, a pumice powder suspension (specific gravity 1.1 g/cm)³) The aluminum plate surface was subjected to mechanical roughening treatment by a rotating bristle brush while being supplied as a polishing slurry.

In the mechanical roughening treatment, the median particle diameter (μm) of the abrasive was set to 30 μm, the number of brushes was set to 4, and the brush rotation speed (rpm) was set to 250 rpm. The bristle brush is made of 6.10 nylon, and has a diameter of 0.3mm and a length of 50 mm. The brush was made dense by drilling holes in a 300mm diameter stainless steel cylinder and tufting. The distance between 2 support rollers (200 mm) below the bristle tuft brush was 300 mm. The tuft brush was pressed until the load of the drive motor rotating the brush was 10kW greater than the load before pressing the tuft brush against the aluminum plate. The direction of rotation of the brush is the same as the direction of movement of the aluminum plate.

(J-b) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 10g/m²。

(J-c) decontamination treatment Using acidic aqueous solution

A waste solution of nitric acid used in the next step of electrochemical graining treatment of an aluminum plate was sprayed with a liquid temperature of 35 ℃ for 3 seconds by a sprayer as an acidic aqueous solution, and desmutting treatment was performed.

(J-d) electrochemical roughening treatment Using nitric acid aqueous solution

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. As the electrolyte, an electrolyte having an aluminum ion concentration of 4.5g/L and a liquid temperature of 35 ℃ was used by adding aluminum nitrate to an aqueous solution of 10.4g/L nitric acid. The ac power waveform was the waveform shown in fig. 1, and the carbon electrode was subjected to electrochemical roughening treatment using a trapezoidal rectangular wave ac with a time tp until the current value reached the peak from zero of 0.8msec and a duty ratio of 1:1 as the counter electrode. Ferrite is used for the auxiliary anode. The electrolytic cell used was one having the structure shown in FIG. 2. The current density was 30A/dm as the peak value of the current²5% of the current from the power supply is shunted to the auxiliary anode. Electric quantity (C/dm)²) The sum of the electric quantity when the aluminum plate is taken as the anode is 185C/dm²。

(J-e) alkali etching treatment

An aluminum plate was etched by spraying an aqueous solution of caustic soda having a caustic soda concentration of 27 mass% and an aluminum ion concentration of 2.5 mass% at a temperature of 50 ℃ with a sprayer. The amount of aluminum dissolved was 3.5g/m²。

(J-f) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution onto an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(J-g) electrochemical roughening treatment Using hydrochloric acid aqueous solution

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. As the electrolyte, an electrolyte having an aluminum ion concentration adjusted to 4.5g/L at a liquid temperature of 35 ℃ was used by adding aluminum chloride to an aqueous solution of 6.2g/L hydrochloric acid. The AC power source waveform is the one shown in FIG. 1, and the current value is used from zero to the peak valueThe time tp of (2) was 0.8msec, the duty ratio was 1:1, and trapezoidal rectangular wave ac was applied to the carbon electrode to perform electrochemical roughening treatment. Ferrite is used for the auxiliary anode. The electrolytic cell used was one having the structure shown in FIG. 2. The current density is 25A/dm in terms of peak value of current²Electric quantity (C/dm) in hydrochloric acid electrolysis²) The sum of the electric quantity when the aluminum plate is taken as the anode is 63C/dm²。

(J-h) alkali etching treatment

An aluminum plate was etched by spraying an aqueous solution of caustic soda having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at a temperature of 60 ℃ with a sprayer. The amount of aluminum dissolved was 0.2g/m²。

(J-i) decontamination treatment Using acidic aqueous solution

The waste liquid (aqueous solution having a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5 g/L) generated in the anodizing treatment step at a liquid temperature of 35 ℃ was sprayed as an acidic aqueous solution onto an aluminum plate for 4 seconds by a sprayer, and the aluminum plate was subjected to desmutting treatment.

(J-J) anodic oxidation treatment of stage 1

The anodic oxidation treatment of stage 1 was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 30A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 0.3g/m²The anodic oxide coating of (1).

(J-k) hole enlarging treatment

The anodized aluminum plate was immersed in a caustic soda aqueous solution having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at a temperature of 40 ℃ for 3 seconds to perform a hole expanding treatment.

(J-l) anodic Oxidation treatment at stage 2

The anodic oxidation treatment of the 2 nd stage was performed by using the anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 13A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.1g/m²Anode oxide scale ofAnd (3) a membrane.

(J-m) hydrophilization treatment

In order to ensure the hydrophilicity of the non-image portion, the aluminum plate was immersed in a 2.5 mass% aqueous solution of sodium silicate No. 3 at 50 ℃ for 7 seconds to carry out silicate treatment. The amount of Si deposited was 8.5mg/m². Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 13 was 30 nm.

< production of support 14 >

The use of a catalyst containing Si: 0.06 mass%, Fe: 0.30 mass%, Cu: 0.005 mass%, Mn: 0.001 mass%, Mg: 0.001 mass%, Zn: 0.001 mass%, Ti: 0.03 mass% and the balance of aluminum and inevitable impurities, and an ingot having a thickness of 500mm and a width of 1,200mm was produced by a DC casting method by treating and filtering the molten metal. After cutting the surface at an average thickness of 10mm by a surface cutter, soaking was performed at 550 ℃ for about 5 hours, and the temperature was lowered to 400 ℃, thereby forming a rolled sheet having a thickness of 2.7mm using a hot rolling mill. Further, after heat treatment at 500 ℃ using a continuous annealing machine, an aluminum plate (width of 1,030mm) of JIS 1050 material was produced by cold rolling to a thickness of 0.24 mm.

The aluminum sheet was subjected to the following surface treatments (b) to (j) continuously to produce the support 14. Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(b) Alkali etching treatment

An aluminum plate was etched by a nebulizer using an aqueous solution having a caustic soda concentration of 2.6 mass%, an aluminum ion concentration of 6.5 mass%, and a temperature of 70 ℃ to dissolve 6g/m 2.

(c) Decontamination treatment

A desmear treatment by a nebulizer was performed with a nitric acid concentration 1 mass% aqueous solution (containing 0.5 mass% of aluminum ions) at a temperature of 30 ℃. The nitric acid aqueous solution used for the desmutting treatment is a waste liquid obtained by performing the step of electrochemical roughening treatment using alternating current in the nitric acid aqueous solution.

(d) Electrochemical roughening treatment

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. The electrolyte is a 10.5g/L aqueous solution of nitric acid (containing 5g/L of aluminum ions and 0.007 mass% of ammonium ions), and the liquid temperature is 50 ℃. The ac power waveform was the waveform shown in fig. 1, and the carbon electrode was subjected to electrochemical roughening treatment using a trapezoidal rectangular wave ac with a time tp until the current value reached the peak from zero of 0.8msec and a duty ratio of 1:1 as the counter electrode. Ferrite is used for the auxiliary anode. The electrolytic cell used was one having the structure shown in FIG. 2. The current density was 30A/dm as the peak value of the current²The total electric quantity when the aluminum plate is used as the anode is 220C/dm². So that 5% of the current flowing from the power supply is shunted to the auxiliary anode.

(e) Alkali etching treatment

An aluminum plate was subjected to a nebulizer-based etching treatment at 32 ℃ using an aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass%, and was dissolved at 0.25g/m ²The method removes aluminum hydroxide-based stains generated when the electrochemical roughening treatment is performed by the preceding-stage alternating current, and dissolves the edge portions of the generated pits to smooth the edge portions.

(f) Decontamination treatment

A sprayer-based desmear treatment was performed with a sulfuric acid concentration 15 mass% aqueous solution (containing 4.5 mass% of aluminum ions) at a temperature of 30 ℃. The nitric acid aqueous solution used for the desmutting treatment is a waste liquid obtained by performing the step of electrochemical roughening treatment using alternating current in the nitric acid aqueous solution.

(g) Electrochemical roughening treatment

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. The electrolyte is 2.5g/L hydrochloric acid aqueous solution (containing 5g/L aluminum ions) and the temperature is 35 ℃. The ac power waveform was the waveform shown in fig. 1, and the carbon electrode was subjected to electrochemical roughening treatment using a trapezoidal rectangular wave ac with a time tp until the current value reached the peak from zero of 0.8msec and a duty ratio of 1:1 as the counter electrode. Ferrite is used for the auxiliary anode. To makeThe electrolytic cell used was the one having the structure shown in FIG. 2. The current density is 25A/dm in terms of peak value of current²The total electric quantity when the aluminum plate is used as the anode is 50C/dm ²。

(h) Alkali etching treatment

An aluminum plate was subjected to a nebulizer-based etching treatment at 32 ℃ using an aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass%, and was dissolved at 0.1g/m²While removing the aluminum hydroxide-based stain generated when the electrochemical roughening treatment is performed by the preceding-stage alternating current, the edge portion of the generated pit is dissolved to smooth the edge portion.

(i) Decontamination treatment

A sprayer-based desmear treatment was performed with a 25 mass% sulfuric acid aqueous solution (containing 0.5 mass% of aluminum ions) at a temperature of 60 ℃.

(j) Anodic oxidation treatment

The anodic oxidation treatment was performed using an anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. An aqueous solution having a sulfuric acid concentration of 170g/L (containing 0.5 mass% of aluminum ions) was used as an electrolyte, and the electrolyte temperature was 38 ℃ and the current density was 30A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.7g/m²The anodic oxide coating of (1). Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 14 was 7 nm.

< production of support body 15 >

An aluminum plate (aluminum alloy plate) made of 1S having a thickness of 0.19mm was immersed in a 40g/L aqueous sodium hydroxide solution at 60 ℃ for 8 seconds to degrease, and then washed with desalted water for 2 seconds. An aluminum plate was placed in an aqueous solution containing 12g/L hydrochloric acid and 38g/L aluminum sulfate (18 g/L water) at a temperature of 33 ℃ and 130A/dm by 15 second communication ²The current density of (2) was subjected to electrochemical roughening treatment. After washing with desalted water for 2 seconds, the aluminum plate was etched with an aqueous sulfuric acid solution of 155g/L at 70 ℃ for 4 seconds to thereby perform desmutting treatment, and washed with desalted water at 25 ℃ for 2 seconds. In 155g/L sulfuric acid aqueous solution, aluminum was addedThe plates were heated at a temperature of 45 ℃ and 22A/dm²The current density of (2) was subjected to anodic oxidation treatment for 13 seconds, and washed with desalted water for 2 seconds. Then, the support 15 was prepared by treating the support with 4g/L of an aqueous solution of polyvinylphosphonic acid at 40 ℃ for 10 seconds, washing the treated support with desalted water at 20 ℃ for 2 seconds, and drying the treated support. The surface roughness Ra of the support 15 was 0.21. mu.m, and the amount of the anodic oxide film was 4g/m². The average diameter of the micropores on the printing-side surface of the support 15 was 7 nm.

< production of support body 16 >

The support 16 was fabricated by subjecting an aluminum plate (aluminum alloy plate) of 1S material having a thickness of 0.3mm to the following treatments (K-a) to (K-K). Further, water washing treatment was performed between all the treatment steps, and liquid discharge was performed by the nip rolls after the water washing treatment.

(K-a) mechanical roughening treatment (brushing method)

Using an apparatus having the structure shown in FIG. 5, a pumice powder suspension (specific gravity 1.1 g/cm) ³) The aluminum plate surface was subjected to mechanical roughening treatment by a rotating bristle brush while being supplied as a polishing slurry.

In the mechanical roughening treatment, the median particle diameter (μm) of the abrasive was set to 30 μm, the number of brushes was set to 4, and the brush rotation speed (rpm) was set to 250 rpm. The bristle brush is made of 6.10 nylon, and has a diameter of 0.3mm and a length of 50 mm. The brush was made dense by drilling holes in a 300mm diameter stainless steel cylinder and tufting. The distance between 2 support rollers (200 mm) below the bristle tuft brush was 300 mm. The tuft brush was pressed until the load of the drive motor rotating the brush was 10kW greater than the load before pressing the tuft brush against the aluminum plate. The direction of rotation of the brush is the same as the direction of movement of the aluminum plate.

(K-b) alkali etching treatment

An etching treatment was performed by spraying a caustic soda aqueous solution having a caustic soda concentration of 26 mass% and an aluminum ion concentration of 6.5 mass% onto an aluminum plate at a temperature of 70 ℃. The amount of aluminum dissolved in the surface subjected to the electrochemical roughening treatment was 10g/m²。

(K-c) decontamination treatment Using acidic aqueous solution

A waste solution of nitric acid used in the next step of electrochemical graining treatment of an aluminum plate was sprayed with a liquid temperature of 35 ℃ for 3 seconds by a sprayer as an acidic aqueous solution, and desmutting treatment was performed.

(K-d) electrochemical roughening treatment Using nitric acid aqueous solution

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. As the electrolyte, an electrolyte having an aluminum ion concentration of 4.5g/L and a liquid temperature of 35 ℃ was used by adding aluminum nitrate to an aqueous solution of 10.4g/L nitric acid. The ac power waveform was the waveform shown in fig. 1, and the carbon electrode was subjected to electrochemical roughening treatment using a trapezoidal rectangular wave ac with a time tp until the current value reached the peak from zero of 0.8msec and a duty ratio of 1:1 as the counter electrode. Ferrite is used for the auxiliary anode. The electrolytic cell used was one having the structure shown in FIG. 2. The current density was 30A/dm as the peak value of the current²5% of the current from the power supply is shunted to the auxiliary anode. Electric quantity (C/dm)²) The sum of the electric quantity when the aluminum plate is taken as the anode is 185C/dm²。

(K-e) alkali etching treatment

An aluminum plate was etched by spraying an aqueous solution of caustic soda having a caustic soda concentration of 27 mass% and an aluminum ion concentration of 2.5 mass% at a temperature of 50 ℃ with a sprayer. The amount of aluminum dissolved was 0.5g/m²。

(K-f) decontamination treatment Using acidic aqueous solution

An aqueous solution having a liquid temperature of 30 ℃ and a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5g/L was sprayed as an acidic aqueous solution onto an aluminum plate by a sprayer for 3 seconds, and a desmutting treatment was performed.

(K-g) electrochemical roughening treatment Using hydrochloric acid aqueous solution

The electrochemical graining treatment was continuously performed using an alternating voltage of 60 Hz. As the electrolyte, an electrolyte having an aluminum ion concentration adjusted to 4.5g/L at a liquid temperature of 35 ℃ was used by adding aluminum chloride to an aqueous solution of 6.2g/L hydrochloric acid. The AC power waveform is the waveform shown in FIG. 1, and is obtained by trapezoidal rectangular wave AC with the time tp for the current value to reach the peak value from zero being 0.8msec and the duty ratio being 1:1The carbon electrode was subjected to electrochemical roughening treatment as a counter electrode. Ferrite is used for the auxiliary anode. The electrolytic cell used was one having the structure shown in FIG. 2. The current density is 25A/dm in terms of peak value of current²Electric quantity (C/dm) in hydrochloric acid electrolysis²) The sum of the electric quantity when the aluminum plate is taken as the anode is 63C/dm²。

(K-h) alkali etching treatment

An aluminum plate was etched by spraying an aqueous solution of caustic soda having a caustic soda concentration of 5 mass% and an aluminum ion concentration of 0.5 mass% at a temperature of 60 ℃ with a sprayer. The amount of aluminum dissolved was 0.1g/m²。

(K-i) decontamination treatment Using acidic aqueous solution

The waste liquid (aqueous solution having a sulfuric acid concentration of 170g/L and an aluminum ion concentration of 5 g/L) generated in the anodizing treatment step at a liquid temperature of 35 ℃ was sprayed as an acidic aqueous solution onto an aluminum plate for 4 seconds by a sprayer, and the aluminum plate was subjected to desmutting treatment.

(K-j) anodic oxidation treatment

The anodic oxidation treatment was performed using an anodic oxidation apparatus of direct current electrolysis having the structure shown in fig. 3. Using 170g/L sulfuric acid solution as electrolyte, at a liquid temperature of 50 deg.C and a current density of 30A/dm²The anodic oxidation treatment was carried out under the conditions of (1) to form a coating amount of 2.4g/m²The anodic oxide coating of (1).

(K-K) hydrophilization treatment

In order to ensure the hydrophilicity of the non-image portion, the aluminum plate was immersed in a 2.5 mass% aqueous solution of sodium silicate No. 3 at 50 ℃ for 7 seconds to carry out silicate treatment. The amount of Si deposited was 8.5mg/m². Then, water washing was performed using a nebulizer. The average diameter of the micropores on the printing-side surface of the support 16 was 7 nm.

< formation of undercoat layer 1 >

On the support (printing surface side), the dry coating amount is 20mg/m²The undercoat layer coating liquid (1) having the following composition was applied to form the undercoat layer 1.

(undercoat layer coating liquid (1))

[ chemical formula 12]

< formation of undercoat layer 2 >

On the support (printing surface side), the dry coating amount is 26mg/m²The undercoat layer coating liquid (2) having the following composition was applied to form the undercoat layer 2.

(undercoat layer coating liquid (2))

[ chemical formula 13]

The undercoat layer is represented by the numerical value below the bracket on the right of each constituent unit in the compound (2) and the numerical value below the bracket on the right of the ethyleneoxy unit represents the number of repetitions.

< formation of undercoat layer 3 >

On the support (printing surface side), the dry coating amount is 20mg/m²The undercoat layer coating liquid (3) having the following composition was applied to form the undercoat layer 3.

(undercoat layer coating liquid (3))

[ chemical formula 14]

The undercoat layer is represented by the numerical value below the bracket on the right of each constituent unit in the compound (2) and the numerical value below the bracket on the right of the ethyleneoxy unit represents the number of repetitions.

< formation of undercoat layer 4 >

On the support (printing surface side), the amount of coating was 0.5mg/m in dry condition²The undercoat layer coating liquid (4) having the following composition was applied to form the undercoat layer 4.

(undercoat layer coating liquid (4))

[ chemical formula 15]

< formation of undercoat layer 5 >

On the support (printing surface side), the dry coating amount is 18mg/m²The undercoat layer coating liquid (5) having the following composition was applied to form the undercoat layer 5.

< coating liquid (5) for undercoat layer >

0.3 part by mass of Polymer U (structure shown below)

60.0 parts by mass of pure water

939.7 parts by mass of methanol

[ chemical formula 16]

< formation of image recording layer 1 >

After an image recording layer coating liquid (1) having the following composition was bar-coated on a support (printing surface side), the resultant was dried at 70 ℃ for 60 seconds to form an image recording layer 1 having a thickness of 0.6. mu.m.

(image recording layer coating liquid (1))

*1: UA510H (Kyoeisha Chemical Co., Ltd., product of Ltd., reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate)

*2: ATM-4E (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd., ethoxylated pentaerythritol tetraacrylate)

*3: the graft copolymer 2 was a polymer particle of a graft copolymer of poly (ethylene glycol) methyl ether methacrylate/styrene/acrylonitrile of 10:9:81, and was a dispersion containing 24 mass% of the particle in a solvent having an n-propanol/water mass ratio of 80/20. And the volume average particle diameter thereof was 193 nm.

*4: klucel M refers to hydroxypropyl cellulose available from Hercules.

*5: irgacure 250 is an iodonium salt available from Ciba specialty Chemicals as a 75% propylene carbonate solution and has iodonium (4-methylphenyl) [4- (2-methylpropyl) phenyl ] -hexafluorophosphate.

*6: byk 336 is a modified dimethylpolysiloxane copolymer available from Byk Chem ie GmbH in 25% xylene/methoxypropyl acetate solution.

*7: Black-XV (Compound described below, manufactured by Yamamoto Chemicals Inc.)

[ chemical formula 17]

< formation of image recording layer 2 >

An image recording layer coating liquid (2) having the following composition was bar-coated on a support (printing surface side) and dried at 100 ℃ for 60 seconds to form an image recording layer 2 having a thickness of 0.6 μm.

(image recording layer coating liquid (2))

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

(Synthesis of Binder Polymer 3)

300g of methyl ethyl ketone was placed in a three-necked flask, and heated to 80 ℃ under a nitrogen stream. In the reaction vessel, a solution containing the following compound 1 was added dropwise over 30 minutes: 50.0g of the following compound 2: 50.0g of Azobisisobutyronitrile (AIBN), 0.7g of Methyl Ethyl Ketone (MEK), and 100g of Methyl Ethyl Ketone (MEK). After the end of the dropwise addition, the reaction was continued for a further 7.5 hours. Then, AIBN0.3g was added, and the reaction was continued for a further 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature to obtain a binder polymer 3. The mass average molecular weight of the binder polymer 3 was 75,000. The composition ratio of the constituent units in the binder 3 was 50: 50.

[ chemical formula 22]

< formation of image recording layer 3 >

On the undercoat layer, an image recording layer coating solution (3) having the following composition was bar-coated and dried at 100 ℃ for 60 seconds to form an image recording layer 3 having a thickness of 1.1 μm.

The image recording layer coating liquid (3) is obtained by mixing and stirring the photosensitive liquid (3) and the microgel liquid (3) described below immediately before coating.

(photosensitive solution (3))

(Synthesis of Binder Polymer (2))

1-methoxy-2-propanol was weighed in a three-necked flask: 78.0g, heated to 70 ℃ under nitrogen. To the reaction vessel, a solution of BLEMMER PME-100 (methoxy diethylene glycol monomethacrylate, Nippon Oil and Fats Company, manufactured by Limited) was added dropwise over 2 hours and 30 minutes: 52.1g, methyl methacrylate: 21.8g, methacrylic acid: 14.2g dipentaerythritol hexa (3-mercaptopropionate): 2.15g, V-601 (dimethyl 2, 2' -azobis (isobutyrate), Wako Pure Chemical industry tris, manufactured by Ltd.): 0.38g, 1-methoxy-2-propanol: 54g of the mixed solution. After completion of the dropwise addition, the temperature was raised to 80 ℃ and the reaction was continued for 2 hours. Adding a mixture of V-601: 0.04g, 1-methoxy-2-propanol: 4g of the mixed solution was heated to 90 ℃ to continue the reaction for 2.5 hours. After the reaction was completed, the reaction solution was cooled to room temperature.

1-methoxy-2-propanol was added to the above reaction solution: 137.2g, 4-hydroxy-tetramethylpiperidine-N-oxide: 0.24g, glycidyl methacrylate: 26.0g, tetraethylammonium bromide: after 3.0g was stirred well, it was heated at 90 ℃.

After 18 hours the reaction solution was cooled to room temperature (25 ℃), after which 1-methoxy-2-propanol: 99.4g was diluted.

In the binder polymer (2) thus obtained, the solid content concentration: 23% by mass and a mass-average molecular weight in terms of polystyrene measured by GPC was 3.5 ten thousand.

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

(microgel solution (3))

1.979 parts of microgel (3) having a solid content concentration of 21.8% by mass (described below)

0.529 part of 1-methoxy-2-propanol

(preparation of microgel (3))

The preparation of the microgel (3) is shown below.

< preparation of polyvalent isocyanate Compound (1) >

To a suspension of 17.78 parts (80 molar equivalents) of isophorone diisocyanate and 7.35 parts (20 molar equivalents) of the following polyphenol compound (1) in ethyl acetate (25.31 parts) was added 0.043 part of bismuth tris (2-ethylhexanoate) (NEOSTANN U-600, NITTOH CHEMICAL co., LTD.) and stirred. The reaction temperature was set at 50 ℃ while the heat generation was suppressed, and the mixture was stirred for 3 hours to obtain an ethyl acetate solution (50 mass%) of the polyvalent isocyanate compound (1).

[ chemical formula 28]

< preparation of microgel (3) >

The following oil phase components and water phase components were mixed and emulsified at 12,000rpm for 10 minutes using a homogenizer. After the obtained emulsion was stirred at 45 ℃ for 4 hours, 5.20 parts of a10 mass% aqueous solution of 1, 8-diazabicyclo [5.4.0] -undec-7-ene-octanoic acid salt (U-CAT SA102, manufactured by San-Apro Ltd.) was added, stirred at room temperature for 30 minutes, and allowed to stand at 45 ℃ for 24 hours. The solid content concentration was adjusted to 21.8% by mass with distilled water, thereby obtaining an aqueous dispersion of the microgel (3). The volume average particle diameter was measured by a light scattering method using a dynamic light scattering type particle diameter distribution measuring apparatus LB-500 (manufactured by HORIBA, LTD.) and was 0.28. mu.m.

(oil phase component)

(component 1) Ethyl acetate 12.0 parts

(component 2) an adduct (50% by mass ethyl acetate solution, manufactured by Mitsui Chemicals, Inc.) obtained by adding trimethylolpropane (6 mol) to xylene diisocyanate (18 mol) and adding methyl side chain polyoxyethylene (1 mol, repeat number of ethylene oxide unit: 90) thereto

3.76 parts

(component 3) polyvalent isocyanate Compound (1) (as a 50% by mass ethyl acetate solution)

15.0 parts of

(component 4) dipentaerythritol pentaacrylate (SR-399, manufactured by Sartomer Company, Inc.) in a 65% by mass ethyl acetate solution (11.54 parts)

(component 5) 4.42 parts of a 10% ethyl acetate solution of a sulfonate surfactant (PIONIN a-41-C, manufactured by Takemoto Oil & Fat co., ltd.) in water

(Water phase component)

46.87 portions of distilled water

< formation of image recording layer 4 >

On the undercoat layer, an image recording layer coating solution (4) having the following composition was bar-coated and dried at 100 ℃ for 60 seconds to form an image recording layer 4 having a thickness of 1.2 μm.

The image recording layer coating liquid (4) is obtained by mixing and stirring the photosensitive liquid (4) and the microgel liquid (4) described below immediately before coating.

(photosensitive solution (4))

(microgel solution (4))

2.243 parts of microgel (4) (solid content concentration 21.8% by mass)

0.600 parts of 1-methoxy-2-propanol

(preparation of microgel (4))

The following shows a method for producing the microgel (4) used in the above-described microgel solution.

< preparation of polyvalent isocyanate Compound (1) >

To a suspension of 17.78 parts (80 molar equivalents) of isophorone diisocyanate and 7.35 parts (20 molar equivalents) of the following polyphenol compound (1) in ethyl acetate (25.31 parts) was added 0.043 part of bismuth tris (2-ethylhexanoate) (NEOSTANN U-600, NITTOH CHEMICAL co., LTD.) and stirred. The reaction temperature was set at 50 ℃ while the heat generation was suppressed, and the mixture was stirred for 3 hours to obtain an ethyl acetate solution (50 mass%) of the polyvalent isocyanate compound (1).

[ chemical formula 29]

< preparation of microgel (4) >

The following oil phase components and water phase components were mixed and emulsified at 12,000rpm for 10 minutes using a homogenizer. After the obtained emulsion was stirred at 45 ℃ for 4 hours, 5.20 parts of a10 mass% aqueous solution of 1, 8-diazabicyclo [5.4.0] -undec-7-ene-octanoic acid salt (U-CAT SA102, manufactured by San-Apro Ltd.) was added, stirred at room temperature for 30 minutes, and allowed to stand at 45 ℃ for 24 hours. The solid content concentration was adjusted to 21.8% by mass with distilled water, thereby obtaining an aqueous dispersion of the microgel (4). The volume average particle diameter was measured by a light scattering method using a dynamic light scattering type particle diameter distribution measuring apparatus LB-500 (manufactured by HORIBA, LTD.) and was 0.28. mu.m.

(oil phase component)

(component 1) Ethyl acetate 12.0 parts

(component 2) an adduct (50% by mass ethyl acetate solution, manufactured by Mitsui Chemicals, Inc.) obtained by adding trimethylolpropane (6 mol) to xylene diisocyanate (18 mol) and adding methyl side chain polyoxyethylene (1 mol, repeat number of ethylene oxide unit: 90) thereto

3.76 parts

(component 3) polyvalent isocyanate Compound (1) (as a 50% by mass ethyl acetate solution)

15.0 parts of

(component 4) dipentaerythritol pentaacrylate (SR-399, manufactured by Sartomer Company, Inc.) in a 65% by mass ethyl acetate solution (11.54 parts)

(component 5) 4.42 parts of a 10% ethyl acetate solution of a sulfonate surfactant (PIONIN a-41-C, manufactured by Takemoto Oil & Fat co., ltd.) in water

(Water phase component)

46.87 portions of distilled water

< Synthesis of adhesive Polymer (6) >

1-methoxy-2-propanol was weighed in a three-necked flask: 78.0g, heated to 70 ℃ under nitrogen. To the reaction vessel, a solution of BLEMMER PME-100 (methoxy diethylene glycol monomethacrylate, Nippon Oil and Fats Company, manufactured by Limited) was added dropwise over 2 hours and 30 minutes: 52.1g, methyl methacrylate: 21.8g, methacrylic acid: 14.2g dipentaerythritol hexa (3-mercaptopropionate): 2.15g, V-601 (dimethyl 2, 2' -azobis (isobutyrate), Wako Pure Chemical industry tris, manufactured by Ltd.): 0.38g, 1-methoxy-2-propanol: 54g of the mixed solution. After completion of the dropwise addition, the temperature was raised to 80 ℃ and the reaction was continued for 2 hours. Adding a mixture of V-601: 0.04g, 1-methoxy-2-propanol: 4g of the mixed solution was heated to 90 ℃ to continue the reaction for 2.5 hours. After the reaction was completed, the reaction solution was cooled to room temperature.

1-methoxy-2-propanol was added to the above reaction solution: 137.2g, 4-hydroxy-tetramethylpiperidine-N-oxide: 0.24g, glycidyl methacrylate: 26.0g, tetraethylammonium bromide: after 3.0g was stirred well, it was heated at 90 ℃.

After 18 hours the reaction solution was cooled to room temperature (25 ℃), after which 1-methoxy-2-propanol: 99.4g was diluted.

In the binder polymer (6) thus obtained, the solid content concentration: 23% by mass, and a weight average molecular weight in terms of polystyrene measured by GPC was 3.5 ten thousand.

[ chemical formula 30]

< Synthesis of adhesive Polymer (7) >

1-methoxy-2-propanol was weighed in a three-necked flask: 78.00g, heated to 70 ℃ under a stream of nitrogen. To the reaction vessel, a solution of BLEMMER PME-100 (methoxy diethylene glycol monomethacrylate, Nippon Oil and Fats Company, manufactured by Limited) was added dropwise over 2 hours and 30 minutes: 52.8g, methyl methacrylate: 2.8g, methacrylic acid: 25.0g dipentaerythritol hexa (3-mercaptopropionate): 6.4g, V-601 (dimethyl 2, 2' -azobis (isobutyrate), Wako Pure Chemical industries, Ltd.): 1.1g, 1-methoxy-2-propanol: 55g of the mixed solution. After completion of the dropwise addition, the temperature was raised to 80 ℃ and the reaction was continued for 2 hours. After 2 hours, a mixture of V-601: 0.11g, 1-methoxy-2-propanol: 1g of the mixed solution was heated to 90 ℃ to continue the reaction for 2.5 hours. After the reaction was completed, the reaction solution was cooled to room temperature.

1-methoxy-2-propanol was added to the above reaction solution: 177.2g, 4-hydroxy-tetramethylpiperidine-N-oxide: 0.28g, glycidyl methacrylate: 46.0g, tetrabutylammonium bromide: after 3.4g was stirred well, heating was carried out at 90 ℃.

After 18 hours, the reaction solution was cooled to room temperature (25 ℃), after which 0.06g of 4-methoxyphenol, 1-methoxy-2-propanol: 114.5g was diluted.

In the binder polymer (7) thus obtained, the solid content concentration: 23% by mass, a polystyrene-equivalent weight average molecular weight measured by GPC was 1.5 ten thousand.

[ chemical formula 31]

[ chemical formula 32]

[ chemical formula 33]

< formation of image recording layer 5 >

An image recording layer 5 having a thickness of 1.2 μm was formed in the same manner as in the formation of the image recording layer 4 except that the amounts of the binder polymer (6) and the binder polymer (7) of the image recording layer coating liquid (4) at the time of forming the image recording layer 4 were changed to 0.2891 parts and 0.4574 parts, respectively.

< formation of image recording layer 6 >

On the undercoat layer, an image recording layer coating solution (6) having the following composition was bar-coated and dried at 100 ℃ for 60 seconds to form an image recording layer 6 having a thickness of 1.1 μm.

The photosensitive liquid (6) and the microgel liquid (6) described below were mixed and stirred immediately before coating to obtain an image-recording layer coating liquid (6).

< photosensitive solution (6) >

[ chemical formula 34]

The numbers below the brackets on the right of the respective constituent units of the binder polymer (2) and the ammonium group-containing polymer indicate the molar ratio. Me represents a methyl group.

[ chemical formula 35]

[ chemical formula 36]

< microgel solution (6) >)

Microgel (6) 1.580 parts

1.455 parts of distilled water

(preparation of microgel (6))

The following shows a method for producing the microgel (6) used in the above-described microgel liquid (6).

As Oil phase components, 10 parts of an adduct of trimethylolpropane and xylene diisocyanate (manufactured by Mitsui Chemicals & SKC Polyurethanes Inc., TAKENATE D-110N), 5.54 parts of dipentaerythritol pentaacrylate (manufactured by Sartomer Company, Inc., SR399), and 0.1 part of PIONIN a-41C (manufactured by Takemoto Oil & Fat co., ltd.) were dissolved in 17 parts of ethyl acetate. 40 parts of a 4 mass% aqueous solution of PVA-205 was prepared as an aqueous phase component. The oil phase component and the water phase component were mixed and emulsified for 10 minutes at 12,000rpm using a homogenizer. The obtained emulsion was added to 25 parts of distilled water, and after stirring at room temperature (25 ℃, the same shall apply hereinafter) for 30 minutes, it was stirred at 50 ℃ for 3 hours. The microgel (2) was prepared by diluting with distilled water so that the solid content concentration of the thus-obtained microgel liquid became 15 mass%. The microgel had an average particle size of 0.2 μm as measured by the light scattering method.

< formation of image recording layer 7 >

An image recording layer aqueous coating solution containing the following thermoplastic polymer particles, an infrared absorber, and polyacrylic acid was prepared, the pH was adjusted to 3.6, and then the coating solution was applied to a support (printing surface side), and dried at 50 ℃ for 1 minute to form an image recording layer 7. The coating amounts of the respective components after drying are shown below.

Thermoplastic Polymer particles 0.7g/m²

IR-011.20X 10 infrared absorber^-4g/m²

Polyacrylic acid 0.09g/m²

The thermoplastic polymer particles, infrared absorber IR-01 and polyacrylic acid used in the image recording layer coating liquid are as follows.

Thermoplastic polymer particles: styrene/acrylonitrile copolymer (molar ratio 50/50), Tg: 99 ℃, volume average particle size: 60nm

Infrared absorber IR-01: an infrared absorber having the following structure

[ chemical formula 37]

Polyacrylic acid Mw: 250,000

< formation of image recording layer 8 >

An image recording layer coating liquid (8) having the following composition was bar-coated on the undercoat layer, and dried at 115 ℃ for 34 seconds by a warm air drying apparatus to form an image recording layer 8 having a thickness of 1 μm.

(image recording layer coating liquid (8))

(Megaface F-780-F DIC Corporation, methyl ethyl ketone 10% by mass solution)

0.490g of a pigment dispersion (having the following structure, solid content concentration 22.5% by mass, methyl ethyl ketone 31% by mass, 1-methoxy-2-propanol 31% by mass, methanol 15.5% by mass)

[ chemical formula 38]

Adhesive Polymer 1

[ chemical formula 39]

Adhesive Polymer 2

[ chemical formula 40]

Adhesive Polymer 3

[ chemical formula 41]

Adhesive Polymer 4

[ chemical formula 42]

Polymerizable compound

[ chemical formula 43]

Infrared absorber

[ chemical formula 44]

[ chemical formula 45]

Sensitization adjuvant

[ chemical formula 46]

Polymerization inhibitor

[ chemical formula 47]

Mercapto compounds

[ chemical formula 48]

Activating and adding agent 1

[ chemical formula 49]

Fluorine-based surfactant

[ chemical formula 50]

Pigment dispersion

< formation of non-photosensitive resin layer 1 >

A non-photosensitive resin layer coating solution (1) having the following composition was applied on the undercoat layer by bar coating, and dried at 100 ℃ for 60 seconds to form a non-photosensitive resin layer (1) having a thickness of 0.5. mu.m.

(non-photosensitive layer coating solution (1))

The adhesive polymer a was a 16 mass% solution of condensation reaction products (mass average molecular weight: 85,000, acid content: 1.64meq/g) of 4 monomers of the following (1) to (4) in MFG/MEK 1/1.

< formation of non-photosensitive resin layer 2 >

The following non-photosensitive resin layer coating liquid (2) was bar-coated on the undercoat layer, and dried at 100 ℃ for 60 seconds to form a non-photosensitive resin layer 2 having a thickness of 1 μm.

The non-photosensitive resin layer coating liquid (2) was prepared in the same manner except that the infrared absorber (1), the polymerization initiator (1), the borate compound (1), and the ultraviolet absorber (1) were removed from the photosensitive liquid (3) in the image recording layer coating liquid (3).

< formation of protective layer 1 >

A protective layer coating solution (1) having the following composition was bar-coated on the image recording layer and dried at 120 ℃ for 60 seconds to form a protective layer 1 having a thickness of 0.18 μm.

(protective layer coating liquid (1))

Polyvinyl alcohol (POVAL PVA105, degree of saponification: 98 to 99 mol%), KURAAY CO., LTD. manufactured)

1.00 part by mass

Polyethylene glycol (PEG4000, manufactured by Tokyo Chemical Industry Co., Ltd.)

0.39 parts by mass

Surfactant (RAPISOL A-80 (described below), manufactured by NOF CORPORATION.)

0.01 part by mass

The amount of water taken as a whole is 10 parts by mass

[ chemical formula 51]

< formation of protective layer 2 >

A protective layer coating solution (2) having the following composition was applied to the image recording layer or the non-photosensitive resin layer by bar coating and dried at 120 ℃ for 60 seconds to form a protective layer 2 having a thickness of 0.18. mu.m.

(protective layer coating liquid (2))

[ chemical formula 52]

(preparation of inorganic layered Compound Dispersion (1))

6.4 parts of synthetic mica SOMASIF ME-100(Co-op chemical Co., Ltd.) was added to 193.6 parts of ion-exchanged water, and the mixture was dispersed with a homogenizer until the volume average particle diameter became 3 μm (laser scattering method) to prepare an inorganic layered compound dispersion (1). The aspect ratio of the dispersed particles is 100 or more.

< formation of protective layer 3 >

A protective layer coating liquid (3) having the following composition was bar-coated on the image recording layer and dried at 120 ℃ for 60 seconds to form a protective layer 3 having a thickness of 0.18 μm.

(protective layer coating liquid (3))

< formation of protective layer 4 >

A protective layer coating liquid (4) having the following composition was bar-coated on the image recording layer and dried at 120 ℃ for 60 seconds to form a protective layer 4 having a thickness of 0.18 μm.

(coating liquid (4) for protective layer)

[ chemical formula 53]

< formation of protective layer 5 >

A protective layer coating liquid (5) having the following composition was bar-coated on the image recording layer and dried at 120 ℃ for 60 seconds to form a protective layer 5 having a thickness of 0.18 μm.

(protective layer coating liquid (5))

[ chemical formula 54]

< formation of protective layer 6 >

A protective layer coating solution (6) having the following composition was applied to the non-photosensitive resin layer by bar coating and dried at 120 ℃ for 60 seconds to form a protective layer 6 having a thickness of 0.18. mu.m.

(protective layer coating liquid (6))

The Pluronic P-84 is an ethylene oxide/propylene oxide block copolymer, and the EMALEX 710 is polyoxyethylene lauryl ether.

< formation of particle-containing layer >

The particle-containing layer was formed by applying and drying the coating liquid prepared in the following manner as described above: the particles described in table a were added to the coating solution corresponding to any one of the image recording layer, the non-photosensitive resin layer, and the protective layer of the particle-containing layer described in table a, with the addition amount thereof adjusted so as to have the in-plane density described in table a.

< formation of Back coating 1 >

The back coat layer 1 having a thickness of 1.0 μm was formed by bar-coating a back coat layer coating liquid (1) having the following composition on the side of the support opposite to the printing surface side and drying at 100 ℃ for 30 seconds.

(Back coating liquid (1))

< formation of Back coating 2 >

The back coating liquid (2) having the following composition was bar-coated on the side of the support opposite to the printing surface side, and dried at 100 ℃ for 120 seconds to form a back coating layer 2 having a thickness of 0.3. mu.m.

(preparation of Back coating liquid (2))

When the above components are mixed and stirred, heat generation starts in about 5 minutes. After reacting for 60 minutes, the following mixed solution was added, thereby preparing a back coating layer coating liquid (2).

< production of original edition for printing >

The support, the undercoat layer, the image recording layer, the non-photosensitive resin layer, the protective layer, and the back coat layer were combined as shown in table a to prepare a printing original plate.

That is, the support, the undercoat layer, the image recording layer, and the protective layer were combined as described in table a to prepare the lithographic printing plate precursors of examples 1 to 35 and 38, the printing waste plate precursors of examples 36 to 37, and the lithographic printing plate precursors of comparative examples 1 to 4. In the lithographic printing plate precursor of example 38, the back coat layer 1 was provided on the side opposite to the printing surface side. In the lithographic printing plate precursor of comparative example 4, the back coat layer 2 was provided on the side opposite to the printing surface side.

In the lithographic printing plate precursors of examples 1 to 35, examples 36 to 37, and comparative examples 1 to 3, the Bekk smoothness of the outermost surface on the side opposite to the printing surface side was 1200 seconds, and the arithmetic average height Sa was 0.1 μm. In the lithographic printing plate precursor of example 38, the Bek k smoothness of the outermost surface on the side opposite to the printing surface side was 80 seconds, and the arithmetic average height Sa was 2.1. mu.m. In the lithographic printing plate precursor of comparative example 4, the Bekk smoothness of the outermost surface on the side opposite to the printing surface side was 1240 seconds, and the arithmetic average height Sa was 0.1 μm.

In table a, the particles described in the column of the types of particles are as follows.

Particle 1: ART PEARL J-4P (average particle diameter: 1.9 μm)

Particle 2: ART PEARL J-5P (average particle diameter: 3.2 μm)

Particle 3: ART PEARL J-6P (average particle diameter: 5.3 μm)

Particle 4: ART PEARL J-3PY (average particle diameter: 1.2 μm)

Particle 5: ART PEARL J-4PY (average particle diameter: 2.2 μm)

Particle 6: ART PEARL J-6PF (average particle diameter: 4 μm)

Particle 7: ART PEARL J-7PY (average particle diameter: 6 μm)

Particle 8: TOSPEARL 120 (average particle size: 2 μm)

Particle 9: TOSPEARL 130 (average particle diameter: 3 μm)

Particle 10: TOSPEARL 145 (average particle diameter: 4.5 μm)

Particle 11: TOSPEARL 2000B (average particle size: 6 μm)

Particle 12: ART PEARL C-800 transparency (average particle diameter: 6 μm)

The following evaluations were made with respect to the obtained printing original plate. The evaluation results are shown in table B.

< development delay prevention >

(1) Original printing plates for on-press development (original lithographic printing plates of examples 1 to 32, 38 and comparative examples 1 to 4 and original printing plates of example 37)

The surface of the printing surface side of the original printing plate was directly contacted with the surface of the opposite side of the printing surface side to laminate a total of 50 sheets, and then the laminated sheets were placed at 35kgf/cm ²Was crimped under pressure for 8 days. In the original printing plate subjected to this operation, the original lithographic printing plate was mounted on a Trendsetter3244 manufactured by Creo corporation, and the resolution was 2,400dpi, the output was 7W, the outer drum rotation speed was 150rpm, and the plate surface energy was 110mJ/cm²The image exposure was performed under the conditions of (1). The lithographic printing plate precursor after image exposure and the waste printing plate precursor without image exposure were mounted on a TOKYO KIKAI SEISAKUSHO ltd offset rotary press, and printing paper was printed at a speed of 100,000 sheets/hour using inkec co. After the on-press development of the unexposed portion of the image recording layer was completed, the number of sheets of printing paper required until the ink was not transferred to the non-image portion was measured as the number of on-press developed sheets, and the development delay prevention property was evaluated by the following criteria. 5-3 in the allowable range.

5: the number of on-press developed sheets of the original printing plate without press-bonding operation is +3 or less

4: the number of on-press developed sheets of the original printing plate which is not subjected to the pressure welding operation is more than +4 sheets, and the number of on-press developed sheets of the original printing plate which is not subjected to the pressure welding operation is less than +5 sheets

3: the number of on-press developed sheets of the original printing plate which is not subjected to the pressure welding operation is more than +6 sheets, and the number of on-press developed sheets of the original printing plate which is not subjected to the pressure welding operation is less than +10 sheets

2: the number of on-press developed sheets of the original printing plate which is not subjected to the pressure welding operation is more than +11 sheets, and the number of on-press developed sheets of the original printing plate which is not subjected to the pressure welding operation is less than +15 sheets

1: the number of on-press developed sheets of the original printing plate without press-bonding operation +16 or more sheets

(2) Printing original plate for development based on developer (lithographic printing plate original plate of example 33)

The surface of the printing surface side of the original printing plate was directly contacted with the surface of the opposite side of the printing surface side to laminate a total of 50 sheets, and then the laminated sheets were placed at 35kgf/cm²Was crimped under pressure for 8 days. The printing original plate subjected to this operation was exposed to light at an outer drum rotation speed of 1,000rpm (times/minute), a laser output of 70%, and a resolution of 2,400dpi (dot per inch) by Luxel PLATESETTER T-6000III manufactured by Fujifilm Corporation equipped with an infrared semiconductor laser. The exposed image includes a solid image and a 50% dot pattern.

Next, a developing treatment was performed using a developing solution 1 having the following composition and using an automatic developing treatment machine having the structure shown in fig. 4, thereby obtaining a printing plate.

The development processing apparatus shown in fig. 4 is an automatic development processor having 2 rotating brush rollers 111. As the rotating brush roller 111, a brush roller implanted with fibers made of polybutylene terephthalate (the diameter of the bristles is 200 μm, the length of the bristles is 7mm) and having an outer diameter of 55mm was used, and rotated at 120 revolutions per minute (the peripheral speed of the brush tip is 0.94m/s) in the same direction as the conveying direction.

The exposed original printing plate 130 was transported on the transport guide 114 at a transport speed of 60cm/min in the transport direction shown in the figure between 2 pairs of transport rollers 113 from the plate feeding stage 118 to the plate setting stage 119 so that the original printing plate 130 passed between the rotary brush roller 111 and the transport guide 114 opposed thereto.

The developer stored in the developer tank 120 was supplied to the 3 nozzles 115 through the filter 117 and the circulation pump 121 via the pipe 116, and the plate surface was showered and supplied from each nozzle 115. The capacity of the treatment liquid tank 120 was 20 liters, and the developer was recycled. The printing plate discharged from the developing processor is dried by the dryer 122 without being washed with water.

< developer 1 >

(pH：8.5)

[ chemical formula 55]

The number of residual films was counted by observing the obtained printing plate at 5cm × 5cm with a magnifying glass having a magnification of 25 times, and the development retardation prevention property was evaluated by the following criteria. 5-3 in the allowable range.

5: the number of the residual films is 0

4: the number of the residual films is 1-2

3: the number of the residual films is 3-10

2: the number of the residual films is 11-50

1: the number of the residual films is more than 51

(3) Printing original plate for development based on developer (lithographic printing plate original plate of example 34)

The surface of the printing original plate on the printing surface side is directly contacted with the surface on the opposite side of the printing surface side to laminate 50 sheets in totalAfter that, at 35kgf/cm²Was crimped under pressure for 8 days. The printing original plate subjected to this operation was subjected to image exposure and development processing in the same manner as in the developing original plate based on the developer in (2) above to obtain a printing plate. However, the following developer 2 was used as the developer. The resulting printing plate was evaluated for development retardation prevention in the same manner as in the above (2) original plate for development printing based on a developer.

< developer 2 >

(pH：7.0)

[ chemical formula 56]

(4) Original printing plate for development using developer (original lithographic printing plate according to example 35 and original printing plate for printing according to example 36)

The surface of the printing surface side of the original printing plate was directly contacted with the surface of the opposite side of the printing surface side to laminate a total of 50 sheets, and then the laminated sheets were placed at 35kgf/cm²Was crimped under pressure for 8 days. The lithographic printing plate precursor of example 35 on which this operation was performed was mounted on a Trendsetter3244 manufactured by Creo corporation, and the resolution was 2,400dpi, the output was 5W, the outer drum rotation speed was 185rpm, and the plate surface energy was 65mJ/cm²The image exposure was performed under the conditions of (1). The waste plate precursor for printing of example 36 was not subjected to image exposure.

Next, a development treatment was carried out at a development temperature of 30 ℃ at a conveying speed (linear velocity) of 2 m/min using an automatic developing machine LP-1310NewsII manufactured by Fujifilm Corporation. A1: 4 water-diluted solution of HN-D manufactured by Fujifilm Corporation was used as the developer, a 1:1.4 water-diluted solution of FCT-421 was used as the replenisher, and a 1:1 water-diluted solution of HN-GV manufactured by Fujifilm Corporation was used as the finish. The resulting printing plate was evaluated for development retardation prevention in the same manner as in the above (2) original plate for development printing based on a developer.

< prevention of multiple plate feed >

A laminate in which 100 printing original plates were integrated in the same direction without using interleaving paper was attached to an NEC ENGINEERING, LTD. CTP platemaker "amzip setter", and the operation of picking publications one by one from the uppermost portion of the laminate was continuously performed 100 times. The plate separability at this time was evaluated on the following criteria. 5-3 is within the allowable range as the preventive property of multi-time plate feeding.

5: the phenomenon that the next plate is not lifted up when the plate is lifted up is 100%.

4: when the plate rises, the next plate is lifted, and the phenomenon that the next plate can not fall immediately is less than 1 percent of the whole phenomenon.

3: when the plate rises, the next plate is lifted, and the phenomenon that the next plate is not peeled by the 1 st separating action is below 1 percent of the whole phenomenon.

2: when the plate rises, the next plate is lifted, and the phenomenon that the plate is not peeled by the 1 st separating action exceeds 1% to 5% of the whole.

1: when the plate rises, the next plate is lifted up, and the phenomenon that the next plate is not peeled off by the 1 st separating action exceeds 5 percent of the whole phenomenon.

< prevention of projection falling off >

The printing original plate was subjected to humidity conditioning for 2 hours at 25 ℃ and 60% RH, then punched out to 2.5cm × 2.5cm, and mounted on a surface of a printing surface side of an unpressed printing original plate in contact with a surface of the printing surface side of the punched printing original plate opposite to the printing surface side, and subjected to rubbing at a plurality of positions of the printing original plate with a load of 0gf to 1,500gf, and a continuous load TYPE scratch strength tester TYPE-18 manufactured by ltd. The rubbed surface on the printing surface side was observed by the naked eye and a Scanning Electron Microscope (SEM), and the falling-off level of the convex portion on the outermost surface on the printing surface side was evaluated by the following criteria. 5-3 in the allowable range.

5: no shedding at all occurred.

4: in 100 convex parts, the falling is more than 1 and less than 5

3: in 100 convex parts, the falling is more than 5 and less than 10

2: in 100 convex parts, the falling is more than 10 and less than 50

1: the number of the protrusions is 50 or more per 100

< scratch resistance >

(1) Original edition for on-press development

The printing original plate was subjected to humidity conditioning for 2 hours at 25 ℃ and 60% RH, then punched out to 2.5cm × 2.5cm, and mounted on a surface on the printing surface side of an unpressed printing original plate in contact with a surface on the opposite side of the punched printing original plate from the printing surface side, a continuous load TYPE scratch strength tester TYPE-18 manufactured by ltd., and the printing original plate was subjected to scratches at a plurality of positions with a load of 0gf to 1,500 gf. In the original printing plate subjected to scratching, the original lithographic printing plate was mounted on a Trendsetter3244 manufactured by Creo corporation, and the resolution was 2,400dpi, the output was 7W, the outer drum rotation speed was 150rpm, and the plate surface energy was 110mJ/cm²The image exposure was performed under the conditions of (1). The lithographic printing plate precursor after image exposure and the waste printing plate precursor without image exposure were mounted on a TOKYO KIKAI SEISAKUSHO ltd offset rotary press, and printing paper was printed at a speed of 100,000 sheets/hour using INKTEC co. During the printing, 1,000 printed matters were sampled, and the degree of scratch contamination caused by scratches was observed with the naked eye and a 6-magnification magnifier, and the scratch preventive property was evaluated by the following criteria. 5-3 in the allowable range.

5: there was no scratch contamination that could be confirmed by a magnifying glass of 6 magnifications.

4: although it could not be confirmed by naked eyes, there were 1 spot of scratch contamination which could be confirmed by a magnifying glass of 6 magnifications.

3: although it could not be confirmed by naked eyes, there were many scratches and stains that could be confirmed by a magnifying glass of 6 magnifications.

2: there were scratch stains that could be confirmed by the naked eye in many places.

1: there was scratch contamination that could be confirmed by naked eyes on the entire surface.

(2) Developing printing original plate based on developing solution

The printing original plate was subjected to humidity conditioning for 2 hours at 25 ℃ and 60% RH, then punched out to 2.5cm × 2.5cm, and mounted on a surface on the printing surface side of an unpressed printing original plate in contact with a surface on the opposite side of the punched printing original plate from the printing surface side, a continuous load TYPE scratch strength tester TYPE-18 manufactured by ltd., and the printing original plate was subjected to scratches at a plurality of positions with a load of 0gf to 1,500 gf. In the original printing plate subjected to scratching, the original lithographic printing plate was mounted on a Trendsetter3244 manufactured by Creo corporation, and the resolution was 2,400dpi, the output was 7W, the outer drum rotation speed was 150rpm, and the plate surface energy was 110mJ/cm ²The image exposure was performed under the conditions of (1). In the method of describing the developing printing original plate based on the developer in the evaluation of the development delay prevention property, the lithographic printing plate original plate after image exposure and the printing waste plate original plate without image exposure were subjected to development treatment to obtain a printing plate.

The obtained printing plate was mounted on a TOKYO KIKAI sesisakusho, ltd. offset rotary press, and printing paper for newspapers was printed at a speed of 100,000 sheets/hour using INKTEC co. During the printing, 1,000 printed matters were sampled, and the degree of scratch contamination caused by scratches was observed with the naked eye and a 6-magnification magnifier, and the scratch preventive property was evaluated by the following criteria. 5-3 in the allowable range.

5: there was no scratch contamination that could be confirmed by a magnifying glass of 6 magnifications.

4: although it could not be confirmed by naked eyes, there were 1 spot of scratch contamination which could be confirmed by a magnifying glass of 6 magnifications.

3: although it could not be confirmed by naked eyes, there were many scratches and stains that could be confirmed by a magnifying glass of 6 magnifications.

2: there were scratch stains that could be confirmed by the naked eye in many places.

1: there was scratch contamination that could be confirmed by naked eyes on the entire surface.

[ Table 9]

TABLE B

	Development delay preventive property	Prevention of multiple plate feed	Prevention of falling of convex part	Scratch preventive property
					Example 1	5	3	5	5
Example 2	5	4	5	5
					Example 3	4	5	4	5
Example 4	5	3	5	5
					Example 5	5	3	5	5
Example 6	5	5	4	5
					Example 7	5	5	3	5
Example 8	5	3	5	5
					Example 9	5	3	5	5
Example 10	5	5	4	5
					Example 11	5	5	3	5
Example 12	5	5	3	5
					Example 13	5	5	3	3
Example 14	5	5	3	4
					Example 15	5	5	3	5
Example 16	5	5	4	3
					Example 17	5	5	4	4
Example 18	5	5	4	5
					Example 19	5	5	4	5
Example 20	5	5	4	5
					Example 21	5	5	4	5
Example 22	5	5	4	5
					Example 23	5	5	4	5
Example 24	5	5	4	5
					Example 25	5	5	4	5
Example 26	5	5	4	5
					Example 27	5	5	4	5
Example 28	5	5	3	5
					Example 29	5	5	3	5
Example 30	5	5	3	5
					Example 31	5	5	3	5
Example 32	5	5	3	5
					Example 33	5	5	3	5
Example 34	5	5	4	5
					Example 35	5	5	3	5
Example 36	5	3	3	5
					Example 37	5	5	3	5
Example 38	5	3	5	5
					Comparative example 1	5	1	-	2
Comparative example 2	5	1	4	2
					Comparative example 3	1	1	1	5
Comparative example 4	5	1	-	2

As is clear from the results shown in table B, the original printing plate according to the present invention has all excellent properties such as the prevention of multiple feeding, the prevention of projection portions coming off, the prevention of scratches, and the prevention of development delay even when the mount is reduced. On the other hand, it was found that the comparative lithographic printing plate precursor could only obtain a result of a difference of 1 or more in the above characteristics. Further, it is found that both prevention of multiple plate feeding and prevention of development delay cannot be achieved.

In particular, the original plate for on-press development according to the present invention can effectively prevent the delay of on-press development while maintaining excellent prevention of multiple feeding, prevention of projection portions from coming off, and prevention of scratches.

Industrial applicability

Provided are a printing original plate, a printing original plate laminate using the printing original plate, a method for making a printing plate, and a printing method, which are excellent in properties such as prevention of plate feeding, prevention of falling off of projections provided on the outermost surface of the original plate, prevention of scratches caused by the projections provided on the outermost surface of the original plate, and prevention of development delay caused by the projections provided on the outermost surface of the original plate, even when the number of times of the process of taking out the original plate from an integrated body is reduced.

The present invention has been described in detail and with reference to specific embodiments thereof, but it is apparent to one skilled in the art that various changes or modifications can be made therein without departing from the spirit and scope thereof.

The present application claims japanese patent application (japanese patent 2018-185922) based on 2018, 9, 28 and the contents of which are incorporated herein by reference.

Description of the symbols

50-main electrolytic bath, 51-alternating current power supply, 52-radial drum roller, 53a, 53 b-main pole, 54-electrolyte supply port, 55-electrolyte, 56-slit, 57-electrolyte passage, 58-auxiliary anode, 60-auxiliary anode tank, W-aluminum plate, 410-anodizing treatment device, 412-power supply tank, 414-electrolytic treatment tank, 416-aluminum plate, 418, 426-electrolyte, 420-power supply electrode, 422, 428-roller, 424-roller, 430-electrolytic electrode, 432-tank wall, 434-direct current power supply, 111-rotating brush roller, 113-conveying roller, 114-conveying guide plate, 115-spray pipe, 116-pipeline, 117-filter, 118-plate feeding table, 119-plate discharging table, 120-developer tank, 121-circulating pump, 122-dryer, 130-original plate for printing, 1-aluminum plate, 2, 4-roller brush, 3-grinding slurry and 5, 6, 7 and 8-supporting roller.