阅读说明：本技术 平版印刷版前体 (Lithographic printing plate precursor ) 是由 T·比利埃 于 2019-03-19 设计创作，主要内容包括：公开了一种平版印刷版前体,其包括包含可聚合化合物、红外吸收染料、包含三卤代烷基的光引发剂和硼酸盐化合物的涂层。(Disclosed is a lithographic printing plate precursor comprising a coating comprising a polymerizable compound, an infrared absorbing dye, a trihaloalkyl-containing photoinitiator, and a borate compound.)

1. A lithographic printing plate precursor comprising a support and a coating, the coating comprising:

-a polymerizable compound;

-an infrared absorbing compound;

-a borate compound represented by formula I:

formula I

Wherein R is_b ¹、R_b ²、R_b ³And R_b ⁴Independently an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl or heteroaryl group; and M⁺Is selected from Li⁺、Na⁺、K⁺Or an optionally substituted ammonium ion;

-a photoinitiator comprising a trihaloalkyl group;

characterized in that the photoinitiator is an optionally substituted tribromomethyl aryl sulfone.

2. The lithographic printing plate precursor according to claim 1, wherein the aryl group of the optionally substituted tribromomethyl aryl sulfone is substituted with at least one electron donating group in ortho or para position.

3. A printing plate precursor according to any preceding claim wherein the optionally substituted ammonium ion is represented by formula II:

formula II

Wherein

R_n ¹、R_n ²And R_n ³Independently an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl or heteroaryl group or a halogen atom.

4. A printing plate precursor according to any preceding claim wherein R_b ¹、R_b ²、R_b ³And R_b ⁴Independently an optionally substituted aryl or heteroaryl group.

5. The printing plate precursor according to any of the preceding claims, wherein the borate compound is present in an amount of 0.05 to 30 wt%.

6. A printing plate precursor according to any preceding claim wherein the infrared absorbing compound is represented by formula III:

formula III

Wherein

Ar¹And Ar²Independently an optionally substituted aryl group or an aryl group having an optionally substituted cyclic benzene ring,

W¹and W²Independently a sulfur atom or-CM¹⁰M¹¹Group, wherein M¹⁰And M¹¹Independently is an optionally substituted aliphatic hydrocarbon group or an optionally substituted (hetero) aryl group, or wherein M¹⁰And M¹¹Together containing the necessary atoms to form a cyclic structure,

M¹And M²Together containing the necessary atoms to form an optionally substituted cyclic structure,

M³and M⁴Independently represents an optionally substituted aliphatic hydrocarbon group,

M⁵、M⁶、M⁷and M⁸Independently represents hydrogen, halogen or an optionally substituted aliphatic hydrocarbon group,

M⁹represents halogen, optionally substituted aliphatic hydrocarbon, optionally substituted (hetero) aryl, -NR¹R²、-NR¹-CO-R⁶、-NR¹-SO₂-R⁴or-NR¹-SO-R⁵(ii) a Wherein

R¹And R²Independently represent hydrogen, an optionally substituted aliphatic hydrocarbon group or an optionally substituted (hetero) aryl group;

R⁴and R⁶Independently represent-OR⁷、-NR⁸R⁹or-CF₃(ii) a Wherein R is⁷Represents an optionally substituted (hetero) aryl group or an optionally branched aliphatic hydrocarbon group and R⁸And R⁹Independently represents hydrogen, an optionally substituted aliphatic hydrocarbon group or an optionally substituted (hetero) aryl group, or wherein R⁸And R⁹Together containing the necessary atoms to form a cyclic structure;

R⁵represents hydrogen, optionally substituted aliphatic hydrocarbon groups, SO₃ ^-、-COOR¹⁰Or optionally substituted (hetero) aryl; wherein R is¹⁰Represents an optionally substituted (hetero) aryl or aliphatic hydrocarbon group; and is

The infrared absorbing compound may include one or more counter ions to obtain a charge neutral molecule.

7. A method of making a printing plate, the method comprising the steps of:

-imagewise exposing the printing plate precursor as defined in any of the preceding claims to heat and/or IR radiation; thereby forming a lithographic image comprised of image areas and non-image areas;

-developing the exposed precursor.

8. The method according to claim 7, whereby upon imagewise exposing the printing plate precursor, a color change is induced in the image area.

9. The method according to claim 7 or 8, wherein the precursor is developed by mounting the precursor on a plate cylinder of a lithographic printing press and rotating the plate cylinder while feeding fountain solution and/or ink to the precursor.

10. The method of claim 7 or 8, wherein the precursor is developed by applying a gum solution to the precursor.

Technical Field

The present invention relates to a novel lithographic printing plate precursor.

Background

Lithographic printing typically involves the use of a so-called printing master, such as a printing plate mounted on a cylinder of a rotary printing press. The master carries a lithographic image on its surface and a print is obtained by applying ink to the image and then transferring the ink from the master to a receiving material, typically paper. In conventional lithographic printing, ink and an aqueous fountain solution (also called dampening liquid) are supplied to a lithographic image consisting of oleophilic (or hydrophobic, i.e. ink-accepting, water-repelling) areas as well as hydrophilic (or oleophobic, i.e. water-accepting, ink-repelling) areas. In so-called dry offset printing, the lithographic image consists of ink-accepting areas and ink-blocking (ink-repelling) areas, and during dry offset printing, only ink is supplied to the master.

Lithographic masters are typically obtained by image-wise (image-wise) exposure and processing of a radiation-sensitive layer on a lithographic support. Imaging and processing make a so-called lithographic printing plate precursor a printing plate or a master. The radiation-sensitive coating is usually imagewise exposed to heat or light by means of a digitally modulated exposure device, such as a laser, which triggers a (physico-) chemical process, such as ablation (ablation), polymerization, insolubilization by cross-linking of the polymer or by particle coagulation of the thermoplastic polymer latex, solubilization by breaking intermolecular interactions or by increasing the permeability of the development barrier. Although some printing plate precursors are capable of producing a lithographic image immediately after exposure, the most popular lithographic printing plate precursors require wet processing because the exposure produces a difference in solubility between exposed and unexposed areas of the coating or a difference in dissolution rate in the developer. In a positive-working lithographic printing plate precursor, the exposed areas of the coating dissolve in the developer, while the unexposed areas remain resistant to the developer. In negative-working lithographic printing plate precursors, the unexposed areas of the coating are dissolved in a developer, while the exposed areas remain resistant to the developer. Most lithographic printing plate precursors comprise a hydrophobic coating on a hydrophilic support such that the areas that remain resistant to the developer define the ink acceptance of the plate, thus defining the printing areas of the plate, while the hydrophilic support is revealed by the dissolution of the coating at the non-printing areas in the developer.

Photopolymer printing plates rely on a mechanism of action whereby a coating, which typically includes a free radical polymerizable compound, hardens upon exposure. "hardening" means that the coating becomes insoluble or non-dispersible in a developing solution and can be achieved by polymerization and/or crosslinking of the photosensitive coating upon exposure to light. Photopolymer printing plate precursors can be sensitive to blue, green or red light (i.e., wavelength range between 450 nm and 750 nm), to violet light (i.e., wavelength range between 350 nm and 450 nm), or to infrared light (i.e., wavelength range between 750 nm and 1500 nm). Optionally, a heating step is performed after the exposing step to enhance or accelerate the polymerization and/or crosslinking reaction.

Typically, a top layer or protective overcoat over the imageable layer is required to act as an oxygen barrier to provide the desired sensitivity to the printing plate. The top layer typically includes a water soluble or water swellable polymer, such as polyvinyl alcohol. In addition to acting as a barrier to oxygen, the top layer should preferably be easily removable during processing and sufficiently transparent to actinic radiation, for example from 300nm to 450 nm or from 450 nm to 750 nm or from 750 nm to 1500 nm.

The classical workflow of photopolymer printing plates includes: the photopolymer printing plate precursor is first exposed in a violet or infrared platemaking machine, followed by a washing step of the protective overcoat, an alkaline development step, and a washing and gumming step. In the last years there has been a clear progress in the direction of simplification of the work flow, wherein the washing step is eliminated and wherein the processing and sizing steps are carried out in one single step, or wherein the processing is carried out with neutral size and then the sizing is carried out in a second step. Alternatively, on-press processing has become very popular, in which a printing plate is mounted on a press and the coating is developed by interaction with fountain solution and ink supplied to the printing plate during operation of the press. During the first run of the press, the non-image areas are removed from the support and thereby define the non-printing areas of the printing plate.

Optionally, the exposing step is followed by a heating step to enhance or accelerate the polymerization and/or crosslinking reaction and/or to improve the adhesion of the image portion to the substrate. This heating step is believed to selectively crosslink those areas of the coating that are selectively imaged during the exposing step so that they do not preferentially dissolve in the developer. As a result, the robustness in terms of plate pressing, i.e., the press life, is significantly improved.

The press life of photopolymer plates is further related to the adhesion strength within the polymerized photolayer. The higher the adhesion strength, the higher the print life. The adhesion strength may preferably be improved by increasing the degree of crosslinking and/or by supramolecular non-covalent interactions such as H-bonds, van der waals interactions and dipole-dipole interactions. The press life of photopolymer printing plates can also be improved by post-irradiating and/or heating the image formed on the support after the development and/or gumming step (also known as "baking" or "post-baking"). Typically, this post-baking step is performed by heating the plate in a large heating oven at a temperature of about 235 ℃ to 290 ℃ for a relatively long time of about 2 to 5 minutes, even up to 10 minutes. This method can significantly extend the life of the printing plate on the printing press.

EP 1910082 discloses a heat-sensitive lithographic printing plate precursor comprising a coating comprising an infrared absorbing dye capable of forming a color upon IR exposure or heating, thereby obtaining a visual contrast between image areas and non-image areas. This visual contrast can be further improved by including borate in the coating.

US 4,772,530 and US 4,772,541 disclose a composition comprising as photoinitiator triphenylbutyl borate or trimethoxyphenylbutyl borate anions which generate free radicals upon exposure to actinic light.

US 4,950,581 discloses a photopolymerizable composition comprising a polymerizable monomer capable of being photopolymerized by active light, a photopolymerizable borate initiator containing at least one alkyl group and an organic nonionic dye.

EP 1467250 discloses a photosensitive composition containing an infrared absorber, a borate initiator compound comprising at least one alkyl group, a polymerizable compound, a binder polymer and a compound having a weight average molecular weight of not more than 3,000 and containing at least one carboxylic acid group.

WO 2006/127313 discloses a negative-working printing plate precursor comprising a free-radically polymerizable element, an initiator system and a tetraarylborate salt.

Disclosure of Invention

It is therefore an object of the present invention to provide a method for manufacturing a heat-sensitive printing plate based on photopolymerization, which method provides excellent sensitivity and/or good storage stability, herein also referred to as shelf life.

Good shelf life refers to no/limited loss of sensitivity, and/or no/limited defect formation in the coating, and/or no/limited tendency to tint over time. This has been evaluated by the aging test described in the examples.

This object is achieved by a printing plate precursor as defined in claim 1 and by preferred embodiments as defined in the dependent claims. A particular feature of the present invention is that the printing plate material comprises a coating comprising a photopolymerizable composition comprising a polymerization initiator and a borate compound, the polymerization initiator being a trihaloalkyl sulfone initiator.

It has surprisingly been observed that the properties of the printing plate precursor according to the invention remain stable upon heat and/or light exposure, even after long term storage of the unexposed precursor. By long term storage is meant, for example, storage for at least six months, but depending on storage conditions, such as temperature and humidity. It is believed that the particular combination of borate compound and trihaloalkyl sulfone initiator prevents degradation and/or deactivation of the initiator, whereby on exposure polymerization at these degraded/deactivated areas is reduced or even prevented and so-called pinholes are formed and/or made visible after processing (especially gumming and/or on-press processing).

It is another object of the present invention to provide a method of preparing a lithographic printing plate, the method comprising the steps of:

-imagewise exposing the printing plate precursor comprising the coating as defined above to heat and/or IR radiation;

-developing the exposed precursor.

The development is preferably carried out by treating the precursor with a gum solution and/or by mounting the precursor on a plate cylinder of a lithographic printing press and rotating the plate cylinder while feeding fountain solution and/or ink to the precursor.

Other features, elements, steps, characteristics and advantages of the present invention will become more apparent from the following detailed description of preferred embodiments of the present invention. Particular embodiments of the invention are also defined in the dependent claims.

Detailed Description

The lithographic printing plate precursor of the present invention comprises a coating comprising a photopolymerizable layer comprising both a borate compound and a trihaloalkyl sulfone initiator (further also referred to as "TBM initiator").

Borate compounds

The borate compound present in the coating layer refers to a compound comprising a borate anion and a cation as a counter ion. Preferably, the borate anion is a tetrahedral boron anion. The borate compound is preferably represented by the following formula I:

Formula I

Wherein R is_b ¹、R_b ²、R_b ³And R_b ⁴Independently an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl or heteroaryl group; and M⁺Being alkali metal cations, e.g. Li⁺、Na⁺、K⁺Optionally substituted ammonium ions, preferably according to formula II:

formula II

Wherein

R_n ¹、R_n ²And R_n ³Independently an optionally substituted aliphatic hydrocarbon group, an optionally substituted aryl or heteroaryl group or a halogen atom.

In a preferred embodiment, R_b ¹、R_b ²、R_b ³And R_b ⁴Independently is optionally substituted aryl or heteroaryl, and M⁺Being alkali metal cations, e.g. Li⁺、Na⁺、K⁺Or an optionally substituted ammonium ion according to formula II. More preferably, R_b ¹、R_b ²、R_b ³And R_b ⁴Independently an optionally substituted aryl group. M⁺Preferably an alkali metal cation, such as Li⁺、Na⁺、K⁺Most preferably Na⁺。

In a highly preferred embodiment, the borate compound comprises at least one optionally substituted phenyl group, more preferably at least two optionally substituted phenyl groups, even more preferably at least three optionally substituted phenyl groups, and most preferably four optionally substituted phenyl groups. The counterion is most preferably an alkali metal cation, such as Li⁺、Na⁺、K⁺Most preferably Na⁺。

The borate compound may be used alone or as a mixture of two or more thereof. As for the content, the borate compound is preferably present in an amount of 0.05 to 30% by weight, more preferably 0.1 to 25% by weight, and most preferably 0.5 to 15% by weight, relative to the total solids of the photopolymerizable layer.

The optionally substituted aryl is preferably optionally substituted phenyl, benzyl, tolyl or o-, m-or p-xylyl, naphthyl, anthryl, phenanthryl and/or combinations thereof. The optionally substituted heteroaryl group is preferably a monocyclic or polycyclic aromatic ring comprising carbon atoms and one or more heteroatoms, preferably 1 to 4 heteroatoms independently selected from nitrogen, oxygen, selenium and sulfur, or combinations thereof, in the ring structure. Preferred examples thereof include optionally substituted furyl, pyridyl, pyrimidinyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thienyl, tetrazolyl, thiazolyl, (1,2,3) triazolyl, (1,2,4) triazolyl, thiadiazolyl, thienyl and/or combinations thereof.

Optional substituents represent alkyl, cycloalkyl, alkenyl or cycloalkenyl, alkynyl, aryl or heteroaryl, alkaryl or aralkyl, alkoxy or aryloxy, thioalkyl, thioaryl or thioheteroaryl, hydroxyl, -SH, carboxylic acid groups or alkyl esters thereof, sulfonic acid groups or alkyl esters thereof, phosphonic acid groups or alkyl esters thereof, phosphoric acid groups or alkyl esters thereof, amino, sulfonamido, amido, nitro, nitrile, halogen, or combinations thereof.

Initiator

TBM-initiators are compounds capable of generating free radicals upon exposure, optionally in the presence of a sensitizer. The TBM-initiator is an optionally substituted trihaloalkyl sulfone compound wherein halogen independently represents bromine, chlorine, iodine or fluorine and the sulfone is a compound containing a sulfonyl functionality attached to two carbon atoms.

The TBM-initiator is an optionally substituted trihaloalkylaryl or heteroaryl sulfone compound. The optionally substituted aryl is preferably optionally substituted phenyl, benzyl, tolyl or o-, m-or p-xylyl, naphthyl, anthryl, phenanthryl and/or combinations thereof. The optionally substituted heteroaryl group is preferably a monocyclic or polycyclic aromatic ring comprising carbon atoms and one or more heteroatoms, preferably 1 to 4 heteroatoms independently selected from nitrogen, oxygen, selenium and sulfur, or combinations thereof, in the ring structure. Preferred examples thereof include optionally substituted furyl, pyridyl, pyrimidinyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thienyl, tetrazolyl, thiazolyl, (1,2,3) triazolyl, (1,2,4) triazolyl, thiadiazolyl, thienyl and/or combinations thereof. Preferably, the TBM-initiator is an optionally substituted trihalomethyl aryl sulfone; more preferably tribromomethyl aryl sulfone, most preferably TBM-initiator is optionally substituted tribromomethyl phenyl sulfone.

The phenyl group of the tribromomethylphenyl sulfone is preferably substituted with at least one electron donating group. The phenyl group may be substituted in ortho, para or meta position, preferably in ortho or para position, more preferably in para position. The phenyl group may be substituted with at least one electron donating group, two or more electron donating groups, or at least one electron donating group and one or more other groups. The phenyl group is preferably substituted with one electron donating group, more preferably substituted with one electron donating group at the para or ortho position, and most preferably substituted with one electron donating group at the para position. The electron donating group is preferably selected from hydroxy, alkoxy, alkyl, amino, monoalkylamino, monoarylamino, dialkylamino, diarylamino, trialkylsilyl, -NH (CO) R or-NH (CO) NHR, wherein R is alkyl or aryl, or-O ^-M⁺Wherein M is⁺Is an alkali metal ion, ammonium ion or tetraalkylammonium ion, more preferably a hydroxyl group, alkoxy group or alkyl group, most preferably a hydroxyl group.

The term "alkyl" as used herein refers to all possible variations of each number of carbon atoms in an alkyl group, i.e., methyl, ethyl; for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl, and tert-butyl; for five carbon atoms: n-pentyl, 1-dimethyl-propyl, 2-dimethylpropyl, and 2-methyl-butyl, and the like. Preferably, the alkyl group is preferably C₁To C₆-an alkyl group. Most preferably, alkyl is methyl.

The term "substituted", in for example substituted alkyl, means that the alkyl group may be substituted with atoms other than those typically present in such groups (i.e., carbon and hydrogen). For example, substituted alkyl groups may include halogen atoms or thiol groups. Unsubstituted alkyl groups contain only carbon and hydrogen atoms.

Optional substituents represent alkyl, cycloalkyl, alkenyl or cycloalkenyl, alkynyl, aryl or heteroaryl, alkaryl or aralkyl, alkoxy or aryloxy, thioalkyl, thioaryl or thioheteroaryl, hydroxyl, -SH, carboxylic acid groups or alkyl esters thereof, sulfonic acid groups or alkyl esters thereof, phosphonic acid groups or alkyl esters thereof, phosphoric acid groups or alkyl esters thereof, amino, sulfonamido, amido, nitro, nitrile, halogen, or combinations thereof.

Suitable alkenyl groups are preferably C₂To C₆Alkenyl radicals, such as the vinyl, n-propenyl, n-butenyl, n-pentenyl, n-hexenyl, isopropenyl, isobutenyl, isopentenyl, neopentynyl, 1-methylbutenyl, isohexenyl, cyclopentenyl, cyclohexenyl and methylcyclohexenyl radicals.

Suitable alkynyl groups are preferably C₂To C₆-an alkynyl group; suitable aralkyl groups preferably include one, two, three or more C₁To C₆-phenyl or naphthyl of an alkyl group; suitable alkaryl radicals are preferably C comprising an aryl radical, preferably phenyl or naphthyl₁To C₆-an alkyl group.

The cyclic group or cyclic structure includes at least one ring structure, and may be a monocyclic or polycyclic group, meaning one ring or multiple rings fused together.

The amount of TBM-initiator generally ranges between 0.1% and 30% by weight, preferably between 0.5% and 20% by weight, most preferably between 1% and 10% by weight, relative to the total weight of the non-volatile components of the photopolymerizable composition.

Suitable examples of the polymerization initiator used in the present invention are as follows:

4-hydroxyphenyl-tribromomethyl-sulfone;

2-hydroxyphenyl-tribromomethyl-sulfone;

4-methoxyphenyl-tribromomethyl-sulfone;

2-methoxyphenyl-tribromomethyl-sulfone;

2, 4-dimethoxyphenyl-tribromomethyl-sulfone;

4-tolyl-tribromomethyl-sulfone;

tribromomethyl- [4- (2-hydroxyethoxy) phenyl ] sulfone; and

4- (tribromomethylsulfonyl) -phenoxy-acetic acid.

In addition to TBM-polymerization initiators, other free radical initiators capable of generating free radicals either directly or upon exposure to a photosensitizer may be used in the present invention.

Examples of the polymerization initiator other than the TBM-initiator include onium salts, halomethyl group-containing compounds, peroxides, azo group-based polymerization initiators, azide compounds, and quinonediazides. Among them, onium salts, particularly sulfonium salts, are preferred from the viewpoint of storage stability.

Lithographic printing plate precursor

The lithographic printing plate precursor according to the invention is negative-working, i.e. after exposure and development, the unexposed areas of the coating are removed from the support and define hydrophilic (non-printing) areas, while the exposed coating is not removed from the support and defines oleophilic (printing) areas. The hydrophilic region is defined by a support having a hydrophilic surface or being provided with a hydrophilic layer. The hydrophobic areas are defined by the coating which hardens upon exposure, optionally followed by a heating step. The region having hydrophilic properties refers to a region having a higher affinity for an aqueous solution than for an oleophilic ink; a region with hydrophobic properties refers to a region with a higher affinity for oleophilic inks than for aqueous solutions.

By "hardening" is meant that the coating becomes insoluble or non-dispersible in the developing solution and can be achieved by polymerization and/or crosslinking of the photosensitive coating, optionally followed by a heating step to enhance or accelerate the polymerization and/or crosslinking reaction. In this optional heating step (hereinafter also referred to as "pre-heating"), the printing plate precursor is heated, preferably at a temperature of about 80 ℃ to 150 ℃, and preferably during a residence time of about 5 seconds to 1 minute.

The coating has at least one layer comprising a photopolymerizable composition, also referred to as "photopolymerizable layer". The coating may include an intermediate layer between the support and the photopolymerizable layer. The lithographic printing precursor can be a multilayer imageable element.

The printing plate of the present invention is characterized in that it can be exposed at low energy density, i.e. energy density is lower than 190 mJ/m; preferably between 70 mJ/m and 150 mJ/m; more preferably between 75 mJ/m and 120 mJ/m and most preferably the maximum value 100 mJ/m.

Support body

The lithographic printing plate used in the present invention comprises a support having a hydrophilic surface or provided with a hydrophilic layer. The support is preferably a grained and anodized aluminum support as is well known in the art. Suitable supports are disclosed, for example, in EP 1843203 ([ 0066) ]To [0075 ]]Segment). The surface roughness obtained after the roughening step is generally expressed as the arithmetic mean center line roughness Ra (ISO 4287/1 or DIN 4762) and may vary between 0.05 μm and 1.5 μm. The aluminum substrates of the present invention preferably have an Ra value of less than 0.45 μm, more preferably less than 0.40 μm, and most preferably less than 0.30 μm. The lower limit of the Ra value is preferably about 0.1. mu.m. More details on preferred Ra values for roughened and anodized aluminium support surfaces are described in EP 1356926. Formation of Al by anodization of an aluminum support₂O₃Layer, and anode weight (g/m)²Al formed on the surface of aluminum₂O₃) At 1 g/m²And 8 g/m²To change between. The weight of the anode is preferably more than or equal to 3 g/m²More preferably ≥ 3.5 g/m²And most preferably not less than 4.0g/m²。

The grained and anodized aluminum support may be subjected to a so-called post-anodization treatment, such as treatment with polyvinylphosphonic acid or derivatives thereof, treatment with polyacrylic acid, treatment with potassium fluorozirconate or phosphate, treatment with alkali metal silicates, or combinations thereof. Alternatively, the support may be treated with an adhesion-promoting compound, such as those described in [0010] of EP 1788434 and WO 2013/182328. However, for precursors optimized for use without a pre-heating step, it is preferred to use a grained and anodized aluminum support without any post-anodization.

In addition to an aluminium support, it is also possible to use a plastic support, for example a polyester support, which is provided with one or more hydrophilic layers, as disclosed in, for example, EP 1025992.

Photopolymer coating

The coating has at least one layer comprising a photopolymerizable composition, also referred to as "photopolymerizable layer". The coating may include an intermediate layer between the support and the photopolymerizable layer.

In addition to the TBM-initiator and borate compound described above, the photopolymerizable layer includes an infrared absorbing compound, a polymerizable compound, and optionally a binder. The coating thickness of the photopolymerizable layer is preferably in the range of 0.2 g/m²And 5.0g/m²More preferably 0.4 g/m²And 3.0 g/m²In between, most preferably 0.6 g/m²And 2.2 g/m²In the meantime.

Infrared absorbing compounds

The IR absorbing compound present in the coating is preferably an infrared absorbing dye, also known as an IR dye. The infrared absorbing dye preferably has an absorption maximum above 780 nm up to 1500 nm. Particularly preferred dyes are cyanine, merocyanine, indoaniline, oxonol, pyrylium (pyrilium) and squarylium (squarilium) dyes. Heptamethine cyanine dyes are most preferred. Examples of suitable IR dyes can be found in EP 1359008 paragraphs [0030] to [0032], including the references cited therein. Other suitable sensitizers are disclosed in US 6,410,205, US 5,049,479, EP 1079276, EP 1369232, EP 1369231, EP 1341040, US 2003/0124460, EP 1241002 and EP 1288720.

The concentration of the IR-dye relative to the total dry weight of the coating may be 0.1 to 20.0 wt.%, more preferably 0.5 to 15.0 wt.%, most preferably 1.0 to 10.0 wt.%. According to the present invention, the amount of the infrared dye is preferably 0.1 to 3% by weight, more preferably 0.2 to 1.5% by weight, and most preferably 0.5 to 1% by weight.

The infrared absorbing compound is preferably represented by formula III:

formula III

Wherein

Ar¹And Ar²Independently an optionally substituted aryl group or an aryl group having an optionally substituted cyclic benzene ring,

W¹and W²Independently a sulfur atom or-CM¹⁰M¹¹Group, wherein M¹⁰And M¹¹Independently is an optionally substituted aliphatic hydrocarbon group or an optionally substituted (hetero) aryl group, or wherein M¹⁰And M¹¹Together containing the necessary atoms to form a cyclic structure,

M¹and M²Together containing the necessary atoms to form an optionally substituted cyclic structure, preferably M¹And M²Together containing the necessary atoms to form an optionally substituted 5-membered ring,

M³and M⁴Independently represents an optionally substituted aliphatic hydrocarbon group,

M⁵、M⁶、M⁷and M⁸Independently represents hydrogen, halogen or an optionally substituted aliphatic hydrocarbon group,

M⁹represents halogen, optionally substituted aliphatic hydrocarbon, optionally substituted (hetero) aryl, -NR¹R²、-NR¹-CO-R⁶、-NR¹-SO₂-R⁴or-NR¹-SO-R⁵(ii) a Wherein

R¹And R²Independently represent hydrogen, an optionally substituted aliphatic hydrocarbon group or an optionally substituted (hetero) aryl group;

R⁴And R⁶Independently represent-OR⁷、-NR⁸R⁹or-CF₃(ii) a Wherein R is⁷Represents an optionally substituted (hetero) aryl group or an optionally branched aliphatic hydrocarbon group and R⁸And R⁹Independently represents hydrogen, an optionally substituted aliphatic hydrocarbon group or an optionally substituted (hetero) aryl group, or wherein R⁸And R⁹Together containing the necessary atoms to form a cyclic structure;

R⁵represents hydrogen, optionally substituted aliphatic hydrocarbon groups, SO₃ ^-、-COOR¹⁰Or optionally substituted (hetero) aryl; wherein R is¹⁰Represents an optionally substituted (hetero) aryl or aliphatic hydrocarbon group; and is

The infrared absorbing compound may include one or more counter ions to obtain a charge neutral molecule.

The aliphatic hydrocarbon group preferably represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an alkynyl group; suitable groups thereof are as described above. Suitable hetero (aryl) groups-i.e. suitable aryl or heteroaryl-are as described above.

Suitable examples of optional substituents represent alkyl, cycloalkyl, alkenyl or cycloalkenyl, alkynyl, aryl or heteroaryl, alkaryl or aralkyl, alkoxy or aryloxy, thioalkyl, thioaryl or thioheteroaryl, hydroxyl, -SH, carboxylic acid groups or alkyl esters thereof, sulfonic acid groups or alkyl esters thereof, phosphonic acid groups or alkyl esters thereof, phosphoric acid groups or alkyl esters thereof, amino, sulfonamido, amido, nitro, nitrile, halogen or combinations thereof.

The IR dye may be a neutral, zwitterionic, anionic or cationic dye, depending on the type of substituent and the number of substituents. The dye may have an anionic or acid group selected from the group consisting of-CO 2H, -CONHSO2Rh, -SO2nhcor, -SO2NHSO2Rj, -PO3H2, -OPO3H2, -OSO3H, -S-SO3H or-SO 3H groups or their corresponding salts, wherein Rh, Ri and Rj independently represent an aryl or alkyl group, preferably a methyl group, and wherein said salt is preferably an alkali metal or ammonium salt, including mono-or di-or tri-or tetra-alkylammonium salts.

The IR dyes are preferably represented by one of the following formulae IV to VIII:

formula IV

Formula V

Formula VI

Wherein

X^-Represents halogen, sulfonate, perfluorosulfonate, tosylate, tetrafluoroborate, hexafluorophosphate, arylborate or arylsulfonate; and is

R³、R³' independently represents an optionally substituted alkyl group, preferably methyl or ethyl; or ether groups, preferably-CH₂-CH₂-O-CH₃。

Formula VII

Of the formula VIII

Wherein

M⁺＝Li⁺、Na⁺、K⁺、NH₄ ⁺、R'R''R'''NH⁺Wherein R ', R ", R'" are independently a H atom, an optionally substituted alkyl group or an aryl group;

the infrared absorbing dye preferably has substantially no absorption in the visible wavelength range and is therefore preferably colorless or light colored. The infrared absorbing dye preferably has an absorption maximum above 780 nm up to 1500 nm. However, the infrared absorbing dyes according to formulae III to VIII are colourless or weakly coloured and become coloured when exposed to heat and/or light in the presence of TBM-initiators, or, in other words, a coating comprising at least one of these IR absorbing dyes and a TBM-initiator forms a clear print-out image when exposed to heat and/or light. It is believed that upon exposure, a redox reaction occurs, thereby obtaining a colored oxidized compound. This is of particular interest because the presence of a colorant (such as a dye, pigment or dye precursor) is redundant, thereby eliminating the risk of contamination of the equipment and/or processing fluids. In addition, the elimination of colorants is advantageous from an economic standpoint. Furthermore, since a color change is obtained immediately after the exposure step and thus a print-out image is formed, the printing plate is particularly suitable for on-press development, i.e. development by mounting the precursor on a plate cylinder of a lithographic printing press and rotating the plate cylinder while fountain solution and/or ink is fed onto the coating. Furthermore, the exposure energy required to obtain a printed-out image is lower than systems provided in the art, e.g. below 150 mJ/m, even far below 120 mJ/m; had obtained clear printed-out images at energy levels of about 80 mJ/m to 100 mJ/m. Furthermore, print-out images have been obtained at low IR dye concentrations, for example in amounts of 0.1 to 3 wt.%.

The color difference between the exposed and unexposed areas of the coating can be calculated from the CIE L x a b color coordinates of the exposed areas of the image areas (exposed areas) of the coating and the CIE L x a b color coordinates of the non-image areas (unexposed areas) of the coating and is expressed as Δ E. When the coating is exposed to the low energy density (e.g., 70 mJ/m to 150 mJ/m, more preferably 75 mJ/m to 120 mJ/m, most preferably the maximum value 100 mJ/m), the printed-out image characterized by the CIE 1976 color difference Δ E of at least 3, more preferably at least 3.5 and most preferably at least 4 may be formed. Δ E is the CIE 1976 color distance Δ E, which is defined by the paired euclidean distance of the CIE L a b color coordinates. CIE L a b color coordinates were obtained from reflectance measurements with a geometric configuration of 45/0 (unpolarized), using a CIE 2 ° observer and D50 as the light source. More details are described in CIE S014-4/E: 2007 colorimetric method-part 4: CIE 1976L a b color Spaces and CIE publications and CIE S014-1/E: 2006, CIE Standard Colourometric applicators.

CIE 1976 color coordinates L, a, and b are part of the well-known CIE (Commission International L' Eclairage) system, which also includes the definition C ═ [ (a)²+ (b)²]^1/2And (C) additional chromaticity values. The CIE 1976 color system is described, for example, in "Colorimetry, CIE 116-.

Preferably, the CIE L a b values are measured according to the method ASTM E308-85.

Polymerizable compound

According to a preferred embodiment of the present invention, the polymerizable compound is a polymerizable monomer or oligomer comprising at least one terminal olefinic group, hereinafter also referred to as "free-radically polymerizable monomer". Polymerization involves linking together free-radically polymerizable monomers.

Suitable free-radically polymerizable monomers are disclosed in EP 2916171 [0042] and [0050], and are incorporated herein by reference.

In addition to the TBM-initiator, the coating may optionally further comprise any free radical initiator capable of generating free radicals upon exposure, either directly or in the presence of a sensitizer. Suitable free radical initiators are described on page 15, line 17 to page 16, line 11 of WO 2005/111727 and in EP 1091247 and may include, for example, hexaaryl-bisimidazole compounds (HABI; dimer of triaryl-imidazole), aromatic ketones, aromatic onium salts, organic peroxides, sulfur-containing compounds, ketoxime ester compounds, borate ester compounds, azinium (azinium) compounds, metallocene compounds, active ester compounds and other compounds having a carbon-halogen bond.

The photopolymerizable layer may also comprise a co-initiator. Typically, a co-initiator is used in combination with a free radical initiator. Suitable co-initiators for photopolymer coatings are disclosed in US 6,410,205, US 5,049,479, EP 1079276, EP 1369232, EP 1369231, EP 1341040, US 2003/0124460, EP 1241002, EP 1288720 and in references including the cited documents: chemistry & Technology UV & EB formulation for coatings, inks & paints-volume 3-photoresists for Free radial and cationic polymerization, K.K.Dietliker-P.K.T.Oldring editor-1991-ISBN 0947798161. As described in EP 107792, specific co-initiators may be present in the photopolymerizable layer to further increase sensitivity. Preferred coinitiators are disclosed in EP 2916171 [0051] and are incorporated herein by reference.

Very high sensitivity can be obtained by including sensitizers such as optical brighteners in the coating. Suitable examples of optical brighteners as sensitizers are described in WO 2005/109103 on page 24, line 20 to page 39. Other preferred sensitizers are sensitizers which absorb blue, green or red light with an absorption spectrum between 450 nm and 750 nm. Useful sensitizers may be selected from the sensitizing dyes disclosed in US 6,410,205, US 5,049,479, EP 1079276, EP 1369232, EP 1369231, EP 1341040, US 2003/0124460, EP 1241002 and EP 1288720.

The photopolymerizable layer preferably comprises a binder. The binder may be selected from a wide range of organic polymers. Combinations of different binders may also be used. Useful binders are described on page 17, line 21 to page 19, line 30 of WO 2005/111727, paragraph [0013] of EP 1043627 and page 16, line 26 to page 18, line 11 of WO 2005/029187. Also of interest are particulate binders, for example including homopolymers and copolymers derived from the following monomeric units: styrene, methylstyrene, acrylonitrile, vinyl acetate, vinyl butyral, vinyl alcohol, acrylamide, methylolacrylamide, methylolmethacrylamide, acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, butyl methacrylate, polyethylene glycol acrylate, polypropylene glycol methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and maleic anhydride/vinyl methyl ether copolymers, optionally containing reactive functional groups, such as ethylenically unsaturated groups, i.e., acryloyl, methacryloyl, vinyl, allyl, isocyanate, epoxy, amino, hydroxyl, carboxyl, or anhydride.

The photopolymerizable layer may also comprise particles that increase the resistance of the coating to artificial or mechanical damage. The particles may be inorganic particles, organic particles or fillers as described in e.g. US 7,108,956. Furthermore, spacer particles may be added to the coating. Further details of suitable spacer particles described in EP 2916171 [0053] to [0056] are incorporated herein by reference. The spacer particles may be substituted with one or more reactive groups.

The photopolymerizable layer may also comprise an inhibitor. Specific inhibitors for use in photopolymer coatings are disclosed in US 6,410,205, EP 1288720 and EP 1749240.

The photopolymerizable layer may also comprise an adhesion promoting compound. The adhesion-promoting compound is a compound capable of interacting with the support, preferably a compound having an addition-polymerizable ethylenically unsaturated bond and a functional group capable of interacting with the support. "interaction" is understood to be any type of physical and/or chemical reaction or process whereby a bond is formed between a functional group and a support, which bond may be a covalent, ionic, complex, coordinative or hydrogen bond, and which may be formed by an adsorption process, a chemical reaction, an acid-base reaction, a complex formation reaction or a reaction of chelating groups or ligands. The adhesion promoting compounds described in EP 2916171 [0058] are incorporated herein by reference.

Various surfactants may be added to the photopolymerizable layer to allow or enhance the developability of the precursor; especially developability with gum solution. Both polymeric and small molecule surfactants are preferred, such as nonionic surfactants. More details are described in EP 2916171 [0059], and are incorporated herein by reference.

The coating may include a top layer or protective overcoat on the photopolymerizable layer that acts as an oxygen barrier, including a water soluble or water swellable binder. Printing plate precursors that do not contain a top layer or protective overcoat are also referred to as overcoat-free printing plate precursors. It is well known in the art that low molecular weight species present in air may degrade or even inhibit image formation, and therefore a top layer is typically applied to the coating. The top layer should be easily removable during development, sufficiently adhere to the photopolymerizable layer or optional other layers of the coating, and should preferably not inhibit light transmission during exposure. Preferred binders that can be used for the top layer are polyvinyl alcohol and polymers disclosed in WO 2005/029190, US 6,410,205 and EP 1288720, including the references cited in these patents and patent applications. The most preferred binder for the top layer is polyvinyl alcohol. The polyvinyl alcohol preferably has a degree of hydrolysis ranging between 74 and 99 mole%, more preferably between 88 and 98 mole%. The weight average molecular weight of the polyvinyl alcohol can be measured by the viscosity of a 4 wt.% aqueous solution at 20 ℃ as defined in DIN 53015, and said viscosity value preferably ranges between 2 and 26, more preferably between 2 and 15, most preferably between 2 and 10.

The overcoat may optionally include other ingredients, such as mineral or organic acids, matting agents or wetting agents, as disclosed in EP 2916171, and incorporated herein by reference.

The coating thickness of the optional top layer is preferably in the range of 0.10 g/m²And 1.75 g/m²More preferably 0.15 g/m²And 1.3 g/m²In between, most preferably 0.20 g/m²And 1.0 g/m²In the meantime. In a more preferred embodiment of the invention, the optional top layer has a thickness of between 0.25 g/m²And 1.75 g/m²And comprises polyvinyl alcohol having a degree of hydrolysis ranging between 74 and 99 mol% and a viscosity value, as defined above, ranging between 3 and 26.

According to the present invention, there is also provided a method of manufacturing a negative-working lithographic printing plate, the method comprising the steps of: the printing plate precursor is imagewise exposed and the imagewise exposed precursor is then developed such that the unexposed areas are dissolved in a developer solution. Optionally, after the imaging step, a heating step is performed to enhance or accelerate the polymerization and/or crosslinking reaction. A lithographic printing plate precursor can be prepared by (i) applying a coating as described above on a support and (ii) drying the precursor.

Exposing step

The printing plate precursor is preferably imagewise exposed by means of a laser emitting IR-light. Preferably, the image-wise exposure step is carried out off-press in a plate-making machine, i.e. an exposure device adapted to image-wise expose the precursor with a laser, such as a laser diode emitting at about 830 nm or a Nd YAG laser emitting at about 1060 nm, or by conventional exposure in contact with a mask (mask). In a preferred embodiment of the invention, the precursor is imagewise exposed by means of a laser emitting IR-light.

Preheating step

After the exposing step, the precursor may be preheated in a preheating unit, preferably at a temperature of about 80 ℃ to 150 ℃, and preferably with a residence time of about 5 seconds to 1 minute. Such a preheating unit may comprise heating elements, preferably IR-lamps, UV-lamps, heated air or heated rollers. Such a preheating step may be used for printing plate precursors comprising photopolymerizable compositions to enhance or accelerate the polymerization and/or crosslinking reaction.

Developing step

After the exposure step or the pre-heating step, the printing plate precursor may be processed (developed) when the pre-heating step is present. A pre-rinse step may be performed prior to developing the imaged precursor, particularly for negative-working lithographic printing precursors having a protective oxygen barrier or topcoat. This pre-rinse step may be performed in a separate device or by manually rinsing the imaged precursor with water, or the pre-rinse step may be performed in a washing unit integrated in the processing machine for developing the imaged precursor. The washing liquid is preferably water, more preferably tap water. Further details regarding the washing step are described in EP 1788434 [0026 ].

During the developing step, the unexposed areas of the image-recording layer are at least partially removed, while the exposed areas are not substantially removed. The processing liquid, also called developer, can be applied to the printing form by hand or in an automatic processing device, for example by rubbing with a dipping pad, by dipping, immersion, coating, spin coating, spray coating, pouring onto it. The treatment with the processing liquid may be combined with mechanical friction, for example by means of a rotating brush. Any water-soluble protective layer present is preferably also removed during the development step. Development is preferably carried out in an automated processing unit at a temperature between 20 ℃ and 40 ℃.

In a highly preferred embodiment, the processing steps described above are replaced by an on-press process, wherein the imaged precursor is mounted on a press and processed on-press by: rotating the plate cylinder while feeding fountain solution and/or ink to the coating of precursor to remove the unexposed areas from the support. In a preferred embodiment, only fountain solution is supplied to the printing plate during start-up of the printing press. The ink supply is also switched on after a certain number of revolutions of the plate cylinder, preferably less than 50 revolutions, and most preferably less than 5 revolutions. In an alternative embodiment, the supply of fountain solution and ink can be started simultaneously, or only ink can be supplied during a certain number of revolutions before the supply of fountain solution is switched on.

The processing step can also be carried out by combining the above embodiments, for example, combining development with a processing solution with on-press development by applying ink and/or fountain solution.

Processing liquid

The processing liquid may be an alkaline developer or a solvent-based developer. Suitable alkaline developers have been described in US 2005/0162505. The alkaline developer is an aqueous solution having a pH of at least 11, more typically at least 12, preferably 12-14. Alkaline developers typically contain an alkaline agent to achieve a high pH, and may be inorganic or organic. The developer may comprise anionic, nonionic and amphoteric surfactants (up to 3% by weight of the total composition); biocides (antimicrobials and/or antifungals), antifoams or chelating agents (e.g. alkali gluconates) and thickeners (water-soluble or water-dispersible polyhydroxy compounds, e.g. glycerol or polyethylene glycol).

The processing liquid is preferably a gum solution, whereby during the development step the non-exposed areas of the photopolymerizable layer are removed from the support and the printing plate is gummed in a single step. Developing with a gum solution has the additional benefit that no additional gumming step is required to protect the support surface in the non-printing areas due to residual gum in the unexposed areas on the plate. As a result, the precursor is processed and sized in one single step, which involves a simpler developing device compared to a developing device comprising a developer tank, a rinsing section and a sizing section. The gluing section may comprise at least one gluing unit or may comprise two or more gluing units. These gumming units may have the configuration of a cascade system, i.e. the gum solution used in the second gumming unit and present in the second tank overflows from the second tank to the first tank when the gum make-up solution is added to the second gumming unit or when the gum solution in the second gumming unit is used only once (i.e. when the precursor is developed in this second gumming unit using only the starting gum solution, preferably by spraying or spraying techniques). More details about such gum development are described in EP 1788444.

The gum solution is typically an aqueous liquid comprising one or more surface protective compounds capable of protecting the lithographic image of the printing plate from contamination, such as by oxidation, fingerprints, fats, oils or dust, or from damage, such as by scratching during handling of the printing plate. Suitable examples of such surface protecting compounds are film forming hydrophilic polymers or surfactants. The layer remaining on the printing plate after treatment with the gum solution is preferably comprised between 0.005 g/m²And 20 g/m²More preferably 0.010 g/m²And 10 g/m²More preferably 0.020 g/m²And 5 g/m²A surface protective compound in between. Further details regarding the surface protective compounds in the gum solution can be found on page 9, line 3 to page 11, line 6 of WO 2007/057348. Since the developed printing plate precursor is developed and gummed in one step, the processed printing plate does not require post-treatment.

The gum solution preferably has a pH of from 3 to 11, more preferably from 4 to 10, even more preferably from 5 to 9, and most preferably from 6 to 8. Suitable gum solutions are described, for example, in EP 1342568 [0008] to [0022] and WO 2005/111727. The gum solution may further comprise inorganic salts, anionic surfactants, wetting agents, chelating compounds, antimicrobial compounds, defoaming compounds, and/or ink absorbers and/or combinations thereof. Further details regarding these additional components are described on page 11, line 22 to page 14, line 19 of WO 2007/057348.

Drying and baking step

After the processing step, the printing plate may be dried in a drying unit. In a preferred embodiment, the printing plate is dried by heating the printing plate in a drying unit, which may comprise at least one heating element selected from IR-lamps, UV-lamps, heated metal rolls or heated air.

After drying, the printing plate can optionally be heated in a baking unit and/or irradiated with LED light, preferably UV LED light. Further details regarding the heating in the baking unit can be found on page 44, line 26 to page 45, line 20 of WO 2007/057348.

The printing plate thus obtained can be used for conventional so-called wet offset printing in which ink and an aqueous fountain solution are supplied to the printing plate. Another suitable printing method uses so-called single fluid inks without fountain solution. Suitable single fluid inks have been described in US 4,045,232, US 4,981,517 and US 6,140,392. In a most preferred embodiment, the single fluid ink comprises an ink phase (also referred to as a hydrophobic or oleophilic phase) and a polyol phase, as described in WO 00/32705.