阅读说明：本技术 转印材料、层叠体及层叠体的制造方法 (Transfer material, laminate, and method for producing laminate ) 是由 中村秀之 于 2019-08-08 设计创作，主要内容包括：本发明提供一种转印材料、以及使用上述转印材料的层叠体及层叠体的制造方法,所述转印材料具有临时支承体、以及包含选自由粘合剂聚合物及烯属不饱和化合物组成的组中的至少1种化合物和碳纳米管的感光性层,在上述临时支承体与上述感光性层的界面的至少一部分具有凹凸形状。(The invention provides a transfer material, a laminate using the transfer material and a method for manufacturing the laminate, wherein the transfer material comprises a temporary support and a photosensitive layer containing at least 1 compound selected from the group consisting of a binder polymer and an ethylenically unsaturated compound and carbon nanotubes, and at least a part of the interface between the temporary support and the photosensitive layer has a concave-convex shape.)

1. A transfer material, comprising:

a temporary support; and

a photosensitive layer comprising at least 1 compound selected from the group consisting of a binder polymer and an ethylenically unsaturated compound, and carbon nanotubes,

the temporary support has a concavo-convex shape at least in a part of an interface with the photosensitive layer.

2. The transfer material according to claim 1,

the average height of the protrusions in the concave-convex shape is 150nm to 1000 nm.

3. The transfer material according to claim 1 or 2,

the average pitch of the protrusions in the concave-convex shape is 50nm to 500 nm.

4. The transfer material according to any one of claims 1 to 3,

the average thickness of the photosensitive layer is 5 [ mu ] m or more.

5. The transfer material according to any one of claims 1 to 4,

the content of the carbon nanotubes in the photosensitive layer is 0.5 to 10 mass% with respect to the total mass of the photosensitive layer.

6. The transfer material according to any one of claims 1 to 5,

the average fiber diameter of the carbon nano tube is 8 nm-25 nm.

7. The transfer material according to any one of claims 1 to 6,

the normal reflectance of the side of the photosensitive layer having the uneven shape is 1% or less and the diffuse reflectance is 0.5% or less.

8. The transfer material according to any one of claims 1 to 7,

the photosensitive layer has a hue L value of 2 or less on the side having the uneven shape.

9. The transfer material according to any one of claims 1 to 8,

the photosensitive layer contains an ethylenically unsaturated compound and further contains a photopolymerization initiator.

10. The transfer material according to any one of claims 1 to 9, which is a transfer material for stray light removal of light.

11. A laminate comprising a layer obtained by transferring a photosensitive layer of the transfer material according to any one of claims 1 to 10 onto a support.

12. A laminate comprising a colored layer obtained by transferring and curing the photosensitive layer of the transfer material according to any one of claims 1 to 10 on a support.

13. A method of manufacturing a laminate, comprising:

a step of forming a photosensitive layer on a support using the transfer material according to any one of claims 1 to 10; and

and patterning the photosensitive layer.

Technical Field

The present invention relates to a transfer material, a laminate, and a method for manufacturing a laminate.

Background

In the LED display, it is extremely important to reduce the regular reflectance of the image display section from the viewpoints of improvement of contrast and improvement of image display quality.

For example, as an antireflection member for preventing reflection of light of an LED display, a black antireflection member is known.

As a conventional method for forming a substrate with a black pattern, a method described in patent document 1 can be mentioned.

Patent document 1 describes a method for manufacturing a substrate with a black pattern, which includes the following steps (1) and (2), and satisfies the following condition of formula (a) when the laminate with a black pattern formed in step (2) is subjected to a heat treatment at 200 ℃ to 300 ℃.

(1) A step of sequentially disposing a transparent resin layer and a photosensitive black resin layer on a substrate

(2) A step of forming a laminate with a black pattern by exposing and developing the photosensitive black resin layer through a mask having a pattern

Ra-Rb < 0.5 in the formula (A)

(in the formula (A), Rb represents the reflectance at a wavelength of 550nm of the black pattern region of the laminate with black pattern before heat treatment, and Ra represents the reflectance at a wavelength of 550nm of the black pattern region of the laminate with black pattern after heat treatment.)

Further, as a method for producing carbon nanotubes, a method described in patent document 2 can be cited.

Patent document 2 describes a method for producing a carbon nanotube dispersion, which comprises dissolving a polymer compound in an organic solvent to prepare a polymer compound solution having a viscosity of 20 to 30000cP, and adding and dispersing carbon nanotubes in the polymer compound solution.

A display device described in patent document 3 is known as a conventional display device.

Patent document 3 describes a display device including a1 st substrate having a1 st surface and a2 nd surface opposed to the 1 st surface, a2 nd substrate disposed opposed to the 1 st substrate and having a1 st surface opposed to the 2 nd surface of the 1 st substrate and a2 nd surface opposed to the 1 st surface, and a plurality of light emitting portions provided on the 2 nd surface of the 1 st substrate separately from the 2 nd substrate, wherein a light transmission suppressing layer having a light transmitting portion for transmitting light from the light emitting portions is formed on the 2 nd surface of the 2 nd substrate corresponding to each light emitting portion, and an antireflection layer is formed on the light transmitting portion.

Patent document 1: japanese laid-open patent publication No. 2015-087409

Patent document 2: japanese patent laid-open No. 2007-138109

Patent document 3: japanese patent laid-open No. 2014-209198

Disclosure of Invention

Technical problem to be solved by the invention

An object of one embodiment of the present invention is to provide a transfer material having a low diffuse reflectance and a low normal reflectance.

Another object of another embodiment of the present invention is to provide a laminate using the transfer material and a method for manufacturing the laminate.

Means for solving the technical problem

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

<1> a transfer material having: a temporary support; and a photosensitive layer containing carbon nanotubes and at least 1 compound selected from the group consisting of binder polymers and ethylenically unsaturated compounds, wherein the photosensitive layer has a concavo-convex shape in at least a part of an interface between the temporary support and the photosensitive layer.

<2> the transfer material according to <1>, wherein the average height of the protrusions in the above-mentioned uneven shape is 150nm to 1,000 nm.

<3> the transfer material according to <1> or <2>, wherein an average pitch of the protrusions in the above-mentioned uneven shape is 50nm to 500 nm.

<4> the transfer material according to any one of <1> to <3>, wherein the photosensitive layer has an average thickness of 5 μm or more.

<5> the transfer material according to any one of <1> to <4>, wherein a content of the carbon nanotubes in the photosensitive layer is 0.5% by mass to 10% by mass with respect to a total mass of the photosensitive layer.

<6> the transfer material according to any one of <1> to <5>, wherein the carbon nanotubes have an average fiber diameter of 8nm to 25 nm.

<7> the transfer material according to any one of <1> to <6>, wherein a normal reflectance of the side of the photosensitive layer having the concave-convex shape is 1% or less and a diffuse reflectance is 0.5% or less.

<8> the transfer material according to any one of <1> to <7>, wherein a hue L value of a side of the photosensitive layer having the concave-convex shape is 2 or less.

<9> the transfer material according to any one of <1> to <8>, wherein the photosensitive layer contains an ethylenically unsaturated compound and further contains a photopolymerization initiator.

<10> the transfer material according to any one of <1> to <9>, which is a transfer material for removing stray light of light.

<11> a laminate comprising a layer obtained by transferring a photosensitive layer of the transfer material <1> to <10> onto a support.

<12> a laminate having a colored layer obtained by transferring and curing the photosensitive layer of the transfer material <1> to <10> on a support.

<13> a method for producing a laminate, comprising: a step of forming a photosensitive layer on a support by using the transfer material according to any one of <1> to <10 >; and patterning the photosensitive layer.

Effects of the invention

According to one embodiment of the present invention, a transfer material having a low diffuse reflectance and a low normal reflectance can be provided.

Further, according to another embodiment of the present invention, a laminate using the transfer material and a method for manufacturing the laminate can be provided.

Detailed Description

The present invention will be described in detail below. 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 invention, "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 numerical ranges recited in the present specification, an upper limit or a lower limit recited in a certain numerical range may be replaced with an upper limit or a lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples.

In the labeling of the group (atomic group) in the present invention, the unsubstituted and substituted labels include both unsubstituted and substituted groups. For example, "alkyl" includes not only alkyl having no substituent (unsubstituted alkyl), but also alkyl having a substituent (substituted alkyl).

In the present specification, "total solid content" means the total mass of components excluding the solvent from the total composition of the composition. As described above, the "solid component" refers to a component from which a solvent is removed, and may be a solid or a liquid at 25 ℃.

In the present invention, "mass%" and "weight%" mean the same, and "parts by mass" and "parts by weight" mean the same.

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

In the present invention, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition indicates the total amount of the plurality of substances present in the composition unless otherwise specified.

In the present invention, the term "step" includes not only an independent step but also a step that can achieve a desired purpose even when it cannot be clearly distinguished from other steps.

In the present invention, "(meth) acrylic acid" is a concept including both acrylic acid and methacrylic acid, "(meth) acrylate" is a concept including both acrylate and methacrylate, and "(meth) acryloyl group" is a concept including both acryloyl group and methacryloyl group.

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

In the present invention, unless otherwise specified, the proportion of the structural unit in the resin indicates a molar ratio.

In the present invention, unless otherwise specified, the molecular weight when there is a molecular weight distribution indicates the weight average molecular weight (Mw).

The present invention will be described in detail below.

(transfer Material)

The transfer material of the present invention comprises: a temporary support; and a photosensitive layer containing carbon nanotubes and at least 1 compound selected from the group consisting of binder polymers and ethylenically unsaturated compounds, wherein the photosensitive layer has an irregular shape in at least a part of an interface between the temporary support and the photosensitive layer.

The transfer material of the present invention is preferably a transfer material for removing light stray light, more preferably a transfer material for removing light stray light in a display device, still more preferably a transfer material for removing light stray light in an LED display, and particularly preferably a transfer material for removing light stray light in a micro LED display.

The size (maximum diameter) of the LEDs in the above-described micro LED display is preferably less than 100 μm.

Further, the transfer material of the present invention can be suitably used as a transfer material for forming an antireflection layer.

In the conventional black layer, for example, a black layer having a black layer containing carbon black is known, and in the front member having the black layer, both diffuse reflectance (SCE reflectance) and normal reflectance (SCI reflectance) are high, and for example, when the black layer is used in a display device, visibility of display contents is poor.

As a result of intensive studies, the present inventors have found that a transfer material having both a low diffuse reflectance and a low normal reflectance can be provided by adopting the above-described constitution.

The mechanism of action of the excellent effect by this is not yet clarified, but is presumed as follows.

The light-sensitive layer containing carbon nanotubes and having an uneven surface or the colored layer obtained by curing the light-sensitive layer can suppress the diffuse reflectance by absorbing light diffusely reflected by incident light by the carbon nanotubes, and can suppress the normal reflectance by suppressing regular reflection of incident light and absorbing the regular reflection of incident light by containing carbon nanotubes and having an uneven surface.

The transfer material of the present invention can suppress both regular reflection and diffuse reflection, and therefore can form a layer having excellent antireflection properties, and when used for an antireflection member in a display device, for example, can display a clear black image with little reflection and stray light, and has excellent visibility of display contents.

The transfer material of the present invention will be described in detail below.

< concave-convex shape >

The transfer material of the present invention has a concavo-convex shape in at least a part of an interface between the temporary support and the photosensitive layer.

The uneven shape may be present only in a part of the interface between the temporary support and the photosensitive layer, or may be present in the entire interface.

The shape of the concave-convex itself in the above concave-convex shape is not particularly limited as long as it is a desired shape, and examples thereof include a prismatic shape, a cylindrical shape, a pyramidal shape, a conical shape, a truncated pyramidal shape, a truncated conical shape, an indeterminate shape, and the like.

The irregularities in the above-described irregular shapes may be the same shape or different shapes (similar shape, random shape, etc.).

For example, when the above-described uneven shape is formed using a stamper having a moth-eye structure described later, the uneven shape having a regular shape of the unevenness itself can be easily formed, and when the above-described uneven shape is formed using an ion beam described later, the uneven shape having a random shape of the unevenness can be formed.

From the viewpoint of suppressing the normal reflectance, the average height of the protrusions in the above-described uneven shape is preferably 10nm to 1,500nm, more preferably 50nm to 1,200nm, still more preferably 150nm to 1,000nm, and particularly preferably 150nm to 500 nm.

From the viewpoint of suppressing the normal reflectance, the average pitch of the protrusions in the above-described uneven shape is preferably 10nm to 1,500nm, more preferably 50nm to 500nm, still more preferably 75nm to 400nm, and particularly preferably 100nm to 300 nm.

The average pitch of the projections in the above-described uneven shape represents an average distance between the projections, and more specifically, an average distance on a plane between the central portions of the projections (excluding a distance in the thickness direction).

The average height and the average pitch of the protrusions in the above-described uneven shape were measured by the following methods.

The photosensitive layer was cut in a direction perpendicular to the thickness direction, and the height of the protrusions and the pitch of the protrusions were measured by observing the cross section with a scanning electron microscope. By repeating this operation, the height of at least 100 protrusions and the pitch of at least 100 protrusions are measured, and the average height and the average pitch of the protrusions in the above-described uneven shape are calculated by taking the respective average values.

< photosensitive layer >

The transfer material of the present invention has a photosensitive layer containing carbon nanotubes and at least 1 compound selected from the group consisting of binder polymers and ethylenically unsaturated compounds, and has an irregular shape in at least a part of an interface between the temporary support and the photosensitive layer.

The photosensitive layer is preferably a layer containing an ethylenically unsaturated compound, and more preferably a layer containing an ethylenically unsaturated compound and a photopolymerization initiator.

The photosensitive layer is preferably a negative photosensitive layer. By providing the photosensitive layer, an arbitrary pattern shape can be easily formed in the photosensitive layer after transfer.

Average thickness

From the viewpoint of suppressing the normal reflectance and the diffuse reflectance and saving the space of the formed member, the average thickness of the photosensitive layer is preferably 1 μm or more, more preferably 5 μm or more, further preferably 5 μm or more and 100 μm or less, and particularly preferably 7 μm or more and 50 μm or less.

The average thickness of the photosensitive layer is calculated by measuring the thickness of the photosensitive layer at 10 or more positions on a cross section obtained by cutting the photosensitive layer in a direction perpendicular to the thickness direction with an optical microscope or a scanning electron microscope, and averaging the measured thicknesses.

The thickness of the photosensitive layer can be measured by observing a cross section obtained by cutting the photosensitive layer in a direction perpendicular to the thickness direction with a scanning electron microscope together with the measurement of the average height and the average pitch of the protrusions in the uneven shape.

Carbon nanotubes

The photosensitive layer contains carbon nanotubes.

The carbon nanotube used in the present invention is not particularly limited, and a known carbon nanotube can be used.

The Carbon Nanotube (CNT) is formed by winding a graphene (6-membered ring mesh) sheet into a cylindrical shape, and preferably has a diameter of several nm to 100nm and a length of several nm to several μm.

In addition, the carbon nanotube may have a 5-membered ring structure or a 7-membered ring structure in part, in addition to the 6-membered ring structure of the graphene structure.

The carbon nanotube used in the present invention may be a carbon nanotube at least a part of which is tubular, and may include a carbon nanotube (carbon nanohorn) in which a tube is closed.

Carbon nanotubes are highly ordered, have a high aspect ratio, and have high mechanical strength and thermal conductivity, and thus are preferably used for the photosensitive layer in the present invention.

Currently, carbon nanotubes can be simply synthesized in an amount of gram units.

The Carbon nanotube is basically a Single graphene layer rolled into a Tube shape, and examples thereof include a Multi Wall Carbon Nanotube (MWCNT) and a Single Wall Carbon Nanotube (SWCNT) in which a graphene sheet is rolled into several concentric layers.

SWCNTs are composed of a single layer of graphene sheets bonded into hexagonal shapes (graphite is formed by stacking graphene sheets into a loose cake shape).

The carbon nanotubes have a large surface area, for example, the size of the carbon nanotubes is usually 1,000m in the closed state²G, in the open state, mostly up to 2,000m²/g。

The present inventors speculate that the number of times of light absorption in the photosensitive layer increases depending on the tube shape of the carbon nanotube and the size of the surface area, and that normal reflectance and diffuse reflectance (particularly diffuse reflectance) can be effectively suppressed.

Furthermore, in the carbon nanotube, the orientation of the hexagon of graphene can be oriented in various directions with respect to the axis of the tube, the helical structure generated at this time is called chirality, and the two-dimensional lattice vector from a reference point of a certain 6-membered ring on graphene is called a chirality vector (C)_h). Chiral vector uses 2 basic translation vectors a of two-dimensional hexagonal grid¹And a²As shown below.

C_h＝na¹+ma²

The set of two integers (n, m) is called the chiral index (chiral index) and is used to denote the structure of the nanotube. The diameter and helix angle of the tubes in a carbon nanotube are determined by the chiral index.

The three-dimensional structure of the carbon nanotube is characterized by adopting a tubular carbon atom array structure called an armchair type in the case where n is m and exhibits metallicity, and adopting a tubular carbon atom array structure called a zigzag type in the case where m is 0, and adopting a general tube structure having a helical structure called a chiral type in the cases other than the above, depending on the chiral index. Among the carbon nanotubes, the (n-m) value is a multiple of 3, and shows a metallic property (metallic carbon nanotube), and the value is a value other than the multiple of 3, and shows a semiconductor property (semiconductor carbon nanotube).

In the present invention, carbon nanotubes having a structure of any chiral index can be suitably used.

The carbon nanotube used in the present invention may be a single-walled carbon nanotube or a multi-walled carbon nanotube, but is preferably a single-walled carbon nanotube in terms of suppressing normal reflectance and diffuse reflectance.

The carbon nanotubes used in the present invention may be semiconductor-type carbon nanotubes or metal-type carbon nanotubes, but from the viewpoint of dispersion stability in a dispersion liquid described later and dispersibility in the photosensitive layer, semiconductor-type carbon nanotubes are preferable.

The average fiber diameter of the carbon nanotube is preferably 1nm to 100nm, more preferably 5nm to 50nm, and particularly preferably 8nm to 25nm, from the viewpoint of suppressing normal reflectance and diffuse reflectance.

The average fiber diameter of the carbon nanotubes is measured by the following method.

The cross section of the photosensitive layer or a colored layer obtained by curing the photosensitive layer or the separated carbon nanotubes was observed by scanning through an electron microscope (manufactured by JEOL ltd). In the observation photograph, an average fiber diameter (nm) of the carbon nanotubes was calculated by selecting 100 arbitrary carbon nanotubes, measuring the outer diameters of the carbon nanotubes, and calculating the number average value thereof.

The photosensitive layer may contain 1 kind of carbon nanotube alone, or may contain 2 or more kinds of carbon nanotubes.

The content of the carbon nanotubes in the photosensitive layer is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, even more preferably 1 to 5% by mass, and particularly preferably 1.5 to 4% by mass, based on the total mass of the photosensitive layer, from the viewpoint of suppressing the normal reflectance and the diffuse reflectance.

Dispersing agent

The photosensitive layer preferably contains a dispersant from the viewpoint of suppressing normal reflectance and diffuse reflectance.

The dispersant is preferably a polymer dispersant. The polymer dispersant may also be a polymer dispersant that functions as a binder polymer described later.

Examples of the polymer dispersant include acrylic polymers, styrene polymers, epoxy polymers, amide epoxy polymers, alkyd polymers, phenol polymers, and cellulose polymers.

The polymer dispersant is preferably an alkali-soluble resin, and more preferably a polymer having a carbonyl group.

Among these, from the viewpoint of dispersibility and suppression of normal reflectance and diffuse reflectance, the polymer dispersant is preferably an acrylic polymer, an epoxy polymer, or a cellulose polymer, more preferably an acrylic polymer, and particularly preferably a (meth) acrylic copolymer.

The acrylic polymer can be produced by polymerizing a (meth) acrylic compound, for example.

Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyltoluene, α -methylstyrene, p-methylstyrene and p-ethylstyrene, esters of vinyl alcohol such as acrylamide, acrylonitrile and vinyl n-butyl ether, alkyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, dimethylaminoethyl (meth) acrylates, diethylaminoethyl (meth) acrylates, glycidyl (meth) acrylates, 2,2, 2-trifluoroethyl (meth) acrylates, 2,2, 3, 3-tetrafluoropropyl (meth) acrylates, (meth) acrylic acid, α -bromo (meth) acrylic acid, α -chloro (meth) acrylic acid, β -furyl (meth) acrylic acid, β -styryl (meth) acrylic acid, and mixtures thereof, Maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate, fumaric acid, cinnamic acid, α -cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof.

The acid value of the polymeric dispersant is preferably from 30mgKOH/g to 200mgKOH/g, more preferably from 45mgKOH/g to 150 mgKOH/g.

The weight average molecular weight of the polymeric dispersant is preferably 1,000 to 100 ten thousand, more preferably 4,000 to 20 ten thousand.

The photosensitive layer may contain 1 kind of the dispersant alone, or may contain 2 or more kinds of the dispersants.

The content of the dispersant in the photosensitive layer is not particularly limited, but is preferably 0.05 to 15 mass% with respect to the total mass of the photosensitive layer.

In forming the photosensitive layer, it is preferable to form the photosensitive layer by preparing a carbon nanotube dispersion by dispersing carbon nanotubes and preparing a photosensitive composition described later using the obtained carbon nanotube dispersion.

The carbon nanotube dispersion preferably includes carbon nanotubes and a dispersant, and more preferably includes carbon nanotubes, a dispersant and an organic solvent.

When the viscosity needs to be reduced for coating the obtained dispersion, the dispersion can be diluted with an organic solvent and a polymer can be added to further increase the viscosity, whereby the viscosity can be adjusted to an appropriate viscosity according to the intended use.

Can be used to prepare the above dispersions. The organic solvent is not particularly limited, and methanol, ethanol, acetone, methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, toluene, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof can be preferably used.

The organic solvent may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

The content of the carbon nanotubes in the carbon nanotube dispersion is not particularly limited, and may be appropriately adjusted depending on the dispersion state or the desired concentration.

When the carbon nanotubes are added, a good dispersion can be obtained by deagglomerating the aggregate and dispersing while preventing re-agglomeration, and it is preferable to impart a sufficient shear force at the time of dispersion.

The dispersion of the carbon nanotubes may be performed while setting the filling level of the carbon nanotubes, and the dispersion may be performed while monitoring the solution by an optical microscope for the purpose of judging aggregation.

As an apparatus that can be used for the dispersion of the carbon nanotubes, an apparatus using an ultrasonic mixing technique or a high shear mixing technique is particularly preferable, and a dispersion can be obtained by emulsification and dispersion by a dispersing mechanism such as a stirrer, a homogenizer, a colloid mill, a jet mixer, a dissolver, a Monton emulsifying apparatus, or an ultrasonic apparatus. The dispersion can also be performed by a treatment using a known pulverization mechanism (for example, ball milling (ball mill, vibration ball mill, planetary ball mill, etc.), sand milling, colloid mill, jet mill, roll mill, etc.). Further, a vertical or horizontal type stirring mill, an attritor, a colloid mill, a ball mill, a 3-roll mill, a bead mill, a super mill, a movable impeller, a disperser, a KD mill, dynatron, a pressure kneader, or the like can be used for pigment dispersion.

Adhesive Polymer

The photosensitive layer preferably contains a binder polymer from the viewpoint of the strength of the photosensitive layer, the maintenance of the uneven shape, and the pattern formability.

Among them, the photosensitive layer particularly preferably contains carbon nanotubes, a binder polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.

The binder polymer is preferably an alkali-soluble resin.

The acid value of the binder polymer is not particularly limited, but from the viewpoint of developability, a binder polymer having an acid value of 60mgKOH/g or more is preferable, an alkali-soluble resin having an acid value of 60mgKOH/g or more is more preferable, and a carboxyl group-containing acrylic resin having an acid value of 60mgKOH/g or more is particularly preferable.

It is presumed that the binder polymer can increase the three-dimensional crosslink density by having an acid value and thermally crosslinking with a compound capable of reacting with an acid by heating. It is also presumed that the carbonyl group of the carbonyl group-containing acrylic resin is dehydrated and hydrophobized, thereby contributing to improvement of the moist heat resistance.

The carbonyl group-containing acrylic resin having an acid value of 60mgKOH/g or more (hereinafter, may be referred to as a specific polymer a.) is not particularly limited if the above-mentioned acid value condition is satisfied, and can be appropriately selected from known resins and used.

For example, a carbonyl group-containing acrylic resin binder polymer having an acid value of 60mgKOH/g or more among the polymers described in paragraph 0025 of Japanese patent application laid-open No. 2011-095716, or a carbonyl group-containing acrylic resin having an acid value of 60mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of Japanese patent application laid-open No. 2010-237589, can be preferably used as the specific polymer A in the present embodiment.

Here, the (meth) acrylic resin means at least one resin containing a structural unit derived from (meth) acrylic acid and a structural unit derived from a (meth) acrylate ester.

The total ratio of the (meth) acrylic acid-derived structural unit and the (meth) acrylate-derived structural unit in the (meth) acrylic resin is preferably 30 mol% or more, and more preferably 50 mol% or more.

The copolymerization ratio of the monomer having a carbonyl group in the specific polymer a is preferably in the range of 5 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 20 to 30% by mass, based on 100% by mass of the specific polymer a.

The specific polymer a may have a reactive group, and examples of a method for introducing a reactive group into the specific polymer a include a method in which an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic anhydride, or the like is reacted with a hydroxyl group, a carbonyl group, a primary amino group, a secondary amino group, an acetoacetyl group, a sulfonic acid, or the like.

Among these, the reactive group is preferably a radical polymerizable group, more preferably an ethylenically unsaturated group, and particularly preferably a (meth) acryloyloxy group.

In addition, the binder polymer, particularly the specific polymer a, preferably has a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.

Examples of the monomer forming the structural unit having an aromatic ring include styrene, tert-butoxystyrene, methylstyrene, α -methylstyrene, benzyl (meth) acrylate, and the like.

The structural unit having an aromatic ring preferably contains at least 1 kind of structural unit represented by the formula P-2 described later. Further, as the structural unit having an aromatic ring, a structural unit derived from a styrene compound is preferable.

When the binder polymer contains a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 50% by mass, based on the total mass of the binder polymer.

In addition, from the viewpoint of adhesiveness and strength after curing, the binder polymer, particularly the specific polymer a, preferably has a structural unit having an alicyclic skeleton.

Specific examples of the structural unit having an alicyclic skeleton include dicyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like.

The alicyclic ring included in the structural unit having an alicyclic skeleton preferably includes a dicyclopentane ring, a cyclohexane ring, an isophorone ring, a tricyclodecane ring, and the like. Among them, a tricyclodecane ring is particularly preferable.

When the binder polymer contains a structural unit having an alicyclic skeleton, the content of the structural unit having an alicyclic skeleton is preferably 5 to 90% by mass, and more preferably 10 to 80% by mass, based on the total mass of the binder polymer.

From the viewpoint of tackiness and strength after curing, the binder polymer, particularly the specific polymer a, preferably has a structural unit having an ethylenically unsaturated group, and more preferably has a structural unit having an ethylenically unsaturated group in a side chain.

In the present invention, the "main chain" represents a relatively longest bonding chain in a molecule of a polymer compound constituting a resin, and the "side chain" represents a group of atoms branched from the main chain.

As the ethylenically unsaturated group, (meth) acryloyl group is preferable, and (meth) acryloyloxy group is more preferable.

When the binder polymer contains a structural unit having an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 40% by mass, based on the total mass of the binder polymer.

As the specific polymer a, the following compound a is preferable. The content ratio of each structural unit shown below can be appropriately changed according to the purpose.

[ chemical formula 1]

Compound A

The acid value of the adhesive polymer used in the present invention is preferably 60mgKOH/g or more, more preferably 60mgKOH/g to 200mgKOH/g, still more preferably 60mgKOH/g to 150mgKOH/g, and particularly preferably 60mgKOH/g to 110 mgKOH/g.

In the present specification, the acid value represents a value measured according to the method described in JIS K0070 (1992).

When the binder polymer contains a binder polymer having an acid value of 60mgKOH/g or more, the interlayer adhesiveness between the photosensitive layer and the second resin layer can be improved by containing an acrylic resin having an acid group in the second resin layer, which will be described later, in addition to the above advantages.

The weight average molecular weight of the specific polymer a is preferably 1 ten thousand or more, and more preferably 2 to 10 ten thousand.

In addition, the binder polymer may be appropriately selected from any film-forming resins according to the purpose, in addition to the specific polymer. From the viewpoint of using the transfer film as an electrode protection film of an electrostatic capacitance type input device, a film having good surface hardness and heat resistance is preferable, an alkali-soluble resin is more preferable, and among the alkali-soluble resins, a known photosensitive siloxane resin material and the like can be preferably used.

The binder polymer used in the present invention preferably contains a polymer containing a structural unit having a carboxylic anhydride structure (hereinafter, also referred to as a specific polymer B). By containing the specific polymer B, the developability and the strength after curing are more excellent.

The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.

The ring of the cyclic carboxylic anhydride structure is preferably a 5-to 7-membered ring, more preferably a 5-or 6-membered ring, and still more preferably a 5-membered ring.

Also, the cyclic carboxylic anhydride structure may be fused or bonded with other ring structures to form a polycyclic structure, but preferably does not form a polycyclic structure.

In the case where the cyclic carboxylic anhydride structure is fused or bonded with another ring structure to form a polycyclic structure, as the polycyclic structure, a bicyclic structure or a helical structure is preferable.

In the polycyclic structure, the number of other ring structures fused or bonded to the cyclic carboxylic anhydride structure is preferably 1 to 5, more preferably 1 to 3.

Examples of the other ring structure include a cyclic hydrocarbon group having 3 to 20 carbon atoms, a heterocyclic group having 3 to 20 carbon atoms, and the like.

The heterocyclic group is not particularly limited, but examples thereof include an aliphatic heterocyclic group and an aromatic heterocyclic group.

Further, as the heterocyclic group, a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is particularly preferable.

The heterocyclic group is preferably a heterocyclic group containing at least one oxygen atom (for example, an oxolane ring, an dioxane ring, a dioxane ring, or the like).

The structural unit having a carboxylic anhydride structure is preferably a structural unit containing a 2-valent group obtained by removing 2 hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or is preferably a structural unit in which a 1-valent group obtained by removing 1 hydrogen atom from a compound represented by the following formula P-1 is bonded to the main chain directly or via a 2-valent linking group.

[ chemical formula 2]

In the formula P-1, R^A1aRepresents a substituent, n^1aR is^A1aMay be the same or different.

Z^1aRepresents a 2-valent group forming a ring containing-C (═ O) -O-C (═ O) -. n is^1aRepresents an integer of 0 or more.

As a group consisting of R^A1aThe substituents shown above include the same substituents as those that the carboxylic anhydride structure may have, and preferred ranges are also the same.

As Z^1aThe alkylene group has preferably 2 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.

The partial structure represented by the formula P-1 may be fused or bonded with other ring structures to form a polycyclic structure, but preferably does not form a polycyclic structure.

Examples of the other ring structure mentioned herein include the same ring structures as those mentioned above which may be fused or bonded to the carboxylic anhydride structure, and preferred ranges are also the same.

n^1aRepresents an integer of 0 or more.

At Z^1aWhen n represents an alkylene group having 2 to 4 carbon atoms^1aThe number of carbon atoms is preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.

At n^1aWhen an integer of 2 or more is represented, a plurality of R's are present^A1aMay be the same or different. And, a plurality of R's present^A1aThe ring may be formed by bonding to each other, but preferably the ring is formed by not bonding to each other.

The structural unit having a carboxylic anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic anhydride, still more preferably a structural unit derived from an unsaturated aliphatic cyclic carboxylic anhydride, yet more preferably a structural unit derived from maleic anhydride or itaconic anhydride, and particularly preferably a structural unit derived from maleic anhydride.

Specific examples of the structural unit having a carboxylic anhydride structure are given below, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples.

In the following structural units, Rx represents a hydrogen atom, a methyl group, or CH₂OH group or CF₃Me represents a methyl group.

[ chemical formula 3]

[ chemical formula 4]

The structural unit having a carboxylic anhydride structure is preferably at least 1 type of the structural units represented by any one of the above formulae a2-1 to a2-21, and more preferably 1 type of the structural units represented by any one of the above formulae a2-1 to a 2-21.

From the viewpoint of developability and moisture permeability of the cured film obtained, the structural unit having a carboxylic anhydride structure preferably contains at least one of the structural unit represented by the formula a2-1 and the structural unit represented by the formula a2-2, and more preferably contains the structural unit represented by the formula a 2-1.

The content (total content in the case of 2 or more species) of the structural unit having a carboxylic anhydride structure in the specific polymer B is preferably 0 to 60 mol%, more preferably 5 to 40 mol%, and still more preferably 10 to 35 mol% with respect to the total amount of the specific polymer B.

In the present invention, when the content of the "structural unit" is defined in a molar ratio, the meaning of the "structural unit" is the same as that of the "monomer unit". In the present invention, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The specific polymer B preferably contains at least 1 structural unit represented by the following formula P-2. Thereby, the moisture permeability of the obtained cured film is further reduced, and the strength is further improved.

[ chemical formula 5]

In the formula P-2, R^P1Represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a carbonyl group or a halogen atom, R^P2Represents a hydrogen atom, an alkyl group or an aryl group, and nP represents an integer of 0 to 5. When nP is an integer of 2 or more, 2 or more R exist^P1May be the same or different.

As R^P1Preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carbonyl group, an F atom, a Cl atom, a Br atom or an I atom, more preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a Cl atom or a Br atom.

As R^P2Preferably hydrogen atomThe alkyl group having 1 to 10 carbon atoms or the aryl group having 6 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

The nP is preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.

As the structural unit represented by the formula P-2, a structural unit derived from a styrene compound is preferable.

Examples of the styrene compound include styrene, p-methylstyrene, α -p-dimethylstyrene, p-ethylstyrene, p-t-butylstyrene, and 1, 1-diphenylethylene, with styrene or α -methylstyrene being preferred, and styrene being particularly preferred.

The styrene compound used to form the structural unit represented by the formula P-2 may be only 1 type, or may be 2 or more types.

When the specific polymer B contains a structural unit represented by the formula P-2, the content of the structural unit represented by the formula P-2 in the specific polymer B (the total content in the case of 2 or more species, the same applies hereinafter) is preferably 5 to 90 mol%, more preferably 30 to 90 mol%, and still more preferably 40 to 90 mol% with respect to the total amount of the specific polymer B.

The specific polymer B may contain a structural unit having a carboxylic anhydride structure and at least 1 other structural unit other than the structural unit represented by the formula P-2.

The other structural units preferably do not contain acid groups.

The other structural units are not particularly limited, and structural units derived from a monofunctional ethylenically unsaturated compound may be mentioned.

As the monofunctional ethylenically unsaturated compound, known compounds can be used without particular limitation, and examples thereof include: (meth) acrylic acid derivatives such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and epoxy (meth) acrylate; n-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; derivatives of allyl compounds such as allyl glycidyl ether; and the like.

The content of the other structural units in the specific polymer B (the total content in the case of 2 or more species) is preferably 10 to 100% by mass, and more preferably 50 to 100% by mass, with respect to the total amount of the specific polymer B.

The weight average molecular weight of the binder polymer is not particularly limited, but is preferably more than 3,000, more preferably more than 3,000 and 60,000 or less, and further preferably 5,000 to 50,000.

The binder polymer may be used alone in 1 kind, or may contain 2 or more kinds.

The content of the binder polymer is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, and still more preferably 30 to 70 mass% with respect to the total mass of the photosensitive layer, from the viewpoint of the strength of a colored layer formed by curing the photosensitive layer and the handling properties in the transfer film.

Ethylenically unsaturated Compounds

The photosensitive layer preferably contains an ethylenically unsaturated compound from the viewpoint of pattern formability.

The ethylenically unsaturated compound is a component contributing to photosensitivity (i.e., photocurability) and strength of a colored layer formed by curing the photosensitive layer.

The ethylenically unsaturated compound is a compound having 1 or more ethylenically unsaturated groups.

The photosensitive layer preferably contains an ethylenically unsaturated compound having 2 or more functions as the ethylenically unsaturated compound.

Here, the ethylenically unsaturated compound having 2 or more functions means a compound having 2 or more ethylenically unsaturated groups in one molecule.

As the ethylenically unsaturated group, (meth) acryloyl group is more preferable.

As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.

From the viewpoint of strength after curing, the photosensitive layer preferably contains 3 or more functional ethylenically unsaturated compounds (preferably 3 or more functional (meth) acrylate compounds), and particularly preferably contains 2-functional ethylenically unsaturated compounds (preferably 2-functional (meth) acrylate compounds) and 3 or more functional ethylenically unsaturated compounds (preferably 3 or more functional (meth) acrylate compounds).

The 2-functional ethylenically unsaturated compound is not particularly limited, and can be appropriately selected from known compounds.

Examples of the 2-functional ethylenically unsaturated compound include tricyclodecanedimethanol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, and 1, 6-hexanediol di (meth) acrylate.

More specifically, examples of the 2-functional ethylenically unsaturated compound include tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Co., manufactured by Ltd.), 1, 9-nonanediol diacrylate (A-NOD-N, Shin-Nakamura Chemical Co., manufactured by Ltd.), and 1, 6-hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Co., manufactured by Ltd.).

The ethylenically unsaturated compound having 3 or more functions is not particularly limited, and can be appropriately selected from known compounds.

Examples of the ethylenically unsaturated compound having 3 or more functions include dipentaerythritol (tri/tetra/penta/hexa) (meth) acrylate, pentaerythritol (tri/tetra) (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, isocyanuric acid (meth) acrylate, and a (meth) acrylate compound having a glycerol tri (meth) acrylate skeleton.

Here, "(tri/tetra/penta/hexa) (meth) acrylate" is a concept including tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate, and "(tri/tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., Kayarad (registered trademark) DPCA-20 manufactured by Ltd., Shin-Nakamura Chemical Co., Ltd., A-9300-1CL manufactured by Ltd), (e.g., alkylene oxide-modified compounds of (meth) acrylate compounds (e.g., Nippon Kayaku Co., Ltd., KAYARAD RP-1040 manufactured by Ltd., Shin-Nakamura Chemical Co., Ltd., ATM-35E, A-9300 manufactured by Ltd., EBECRYL (registered trademark) 135 manufactured by DAICEL-ALLNEX LTD., Ltd.), and ethoxylated glycerol triacrylate (e.g., Shin-Nakamura Chemical., Ltd., A-GLY-9E manufactured by Ltd.).

The ethylenically unsaturated compound may also be a urethane (meth) acrylate compound (preferably a 3-or more-functional urethane (meth) acrylate compound).

Examples of the 3-or higher-functional urethane (meth) acrylate compound include 8UX-015A (TAISEI FINE CHEMICAL CO, manufactured by LTD.), UA-32P (Shin-Nakamura Chemical Co., manufactured by Ltd.), UA-1100H (Shin-Nakamura Chemical Co., manufactured by Ltd.), and the like.

Also, from the viewpoint of improving the developability, the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group.

Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carbonyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include a 3 to 4-functional ethylenically unsaturated compound having an acid group (a compound having an acid value of 80 to 120mgKOH/g) obtained by introducing a carbonyl group into a pentaerythritol tri-and tetraacrylate (PETA) skeleton), a 5 to 6-functional ethylenically unsaturated compound having an acid group (a compound having an acid value of 25 to 70mgKOH/g) obtained by introducing a carbonyl group into a dipentaerythritol penta-and hexaacrylate (DPHA) skeleton), and the like.

These ethylenically unsaturated compounds having 3 or more functions of the acid group can be used together with the ethylenically unsaturated compounds having 2 functions of the acid group as required.

As the ethylenically unsaturated compound having an acid group, at least 1 selected from the group consisting of an ethylenically unsaturated compound having 2 or more functions of a carbonyl group and a carboxylic anhydride thereof is preferable. This improves the developability and the strength of the cured film.

The carbonyl group-containing ethylenically unsaturated compound having 2 or more functions is not particularly limited, and can be appropriately selected from known compounds.

As the carbonyl group-containing 2-or more-functional ethylenically unsaturated compound, for example, ARONIX (registered trademark) TO-2349(TOAGOSEI CO., LTD., manufactured by LTD.), ARONIX M-520(TOAGOSEI CO., LTD., manufactured by LTD.), or ARONIX M-510(TOAGOSEI CO., LTD., manufactured by LTD.) can be preferably used.

The ethylenically unsaturated compound having an acid group is preferably a polymerizable compound having an acid group as described in paragraphs 0025 to 0030 of Japanese patent application laid-open No. 2004-239942. The content of this publication is incorporated in the present specification.

The ethylenically unsaturated compound used in the present invention preferably has a weight average molecular weight (Mw) of 200 to 3,000, more preferably 250 to 2,600, still more preferably 280 to 2,200, and particularly preferably 300 to 2,200.

In the ethylenically unsaturated compound used in the photosensitive layer, the content of the ethylenically unsaturated compound having a molecular weight of 300 or less is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on the total ethylenically unsaturated compounds contained in the photosensitive layer.

The ethylenically unsaturated compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the ethylenically unsaturated compound is preferably 1 to 70% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the photosensitive layer.

When the photosensitive layer contains an ethylenically unsaturated compound having an acid group (preferably, an ethylenically unsaturated compound having a carbonyl group and a 2-or more-functional group or a carboxylic anhydride thereof), the content of the ethylenically unsaturated compound having an acid group is preferably 1 to 50% by mass, more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass, based on the total mass of the photosensitive layer.

Photopolymerization initiator

From the viewpoint of pattern formability and sensitivity, the photosensitive layer preferably further contains a photopolymerization initiator, and more preferably further contains the ethylenically unsaturated compound.

The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.

Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator"), a photopolymerization initiator having an α -aminoalkylphenone structure (hereinafter, also referred to as an "α -aminoalkylphenone-based photopolymerization initiator"), a photopolymerization initiator having an α -hydroxyalkylphenone structure (hereinafter, also referred to as an "α -hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as an "acylphosphine oxide-based photopolymerization initiator"), and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as an "N-phenylglycine-based photopolymerization initiator").

The photopolymerization initiator preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, α -hydroxyalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators, and more preferably contains at least 1 selected from the group consisting of oxime-based photopolymerization initiators, α -aminoalkylphenyl ketone-based photopolymerization initiators, and N-phenylglycine-based photopolymerization initiators.

Further, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of Japanese patent application laid-open No. 2011-095716 and paragraphs 0064 to 0081 of Japanese patent application laid-open No. 2015-014783 can be used.

Examples of commercially available photopolymerization initiators include 1- [4- (phenylthio) ] -1, 2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE (registered trade name) OXE-01, manufactured by BASF), 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane -1-ketone (trade name: IRGACURE 907, manufactured by BASF corporation), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) benzyl ] phenyl } -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF corporation), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE 369, manufactured by BASF corporation), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: IRGACURE 1173, manufactured by BASF corporation), 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE 184, manufactured by BASF corporation), 2-dimethoxy-1, 2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF corporation), oxime ester (trade name: Lunar 6, manufactured by DKSH Management Ltd.), and the like.

The photopolymerization initiator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1.0% by mass or more, relative to the total mass of the photosensitive layer.

The content of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the photosensitive layer.

Surface active agent

The photosensitive layer preferably contains a surfactant from the viewpoint of film thickness uniformity.

As the surfactant, any of anionic, cationic, nonionic (nonion) and amphoteric surfactants can be used, but a preferable surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. Further, the following trade names include KP (Shin-Etsu Chemical Co., Ltd., manufactured by Ltd.), Polyflow (KYOEISHA CHEMICAL Co., manufactured by LTD), EF TOP (manufactured by JEMCO Co., Ltd.), Megaface (manufactured by DIC CORPORATION), Fluorad (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflow (ASAHI GLASS CO., manufactured by LTD.), PolyFox (manufactured by OMNOVA Solutions Inc.), SH-8400 (manufactured by Dow Corning Toray Co., Ltd.), and the like.

Further, as the surfactant, the following copolymers can be cited as preferable examples: contains a structural unit A and a structural unit B represented by the following formula I-1, and has a weight average molecular weight (Mw) of 1,000 to 10,000 in terms of polystyrene as measured by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent.

[ chemical formula 6]

In the formula (I-1), R⁴⁰¹And R⁴⁰³Each independently represents a hydrogen atom or a methyl group, R⁴⁰²Represents a linear alkylene group having 1 to 4 carbon atoms, R⁴⁰⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q represent mass percentages representing a polymerization ratio, p represents a numerical value of 10 to 80 mass%, q represents a numerical value of 20 to 90 mass%, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and x represents a bonding position with another structure.

L is preferably a branched alkylene group represented by the following formula (I-2). R in the formula (I-2)⁴⁰⁵An alkyl group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoint of compatibility and wettability with the surface to be coated. The sum of p and q (p + q) is preferably 100% p + q, i.e., 100% by mass.

[ chemical formula 7]

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

The surfactant described in paragraph 0017 of japanese patent No. 4502784 and paragraphs 0060 to 0071 of japanese patent application laid-open No. 2009-237362 may also be used.

The surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The content of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive layer.

Polymerization inhibitor

The photosensitive layer may contain at least 1 polymerization inhibitor.

As the polymerization inhibitor, for example, a thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph 0018 of japanese patent No. 4502784 can be used.

Among them, phenothiazine, phenoxazine, or 4-methoxyphenol can be suitably used.

When the photosensitive layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 3% by mass, more preferably 0.01 to 1% by mass, and still more preferably 0.01 to 0.8% by mass, based on the total mass of the photosensitive layer.

Hydrogen donating compound

The photosensitive layer preferably further contains a hydrogen donating compound.

In the present invention, the hydrogen-donating compound has an action of further improving the sensitivity of the photopolymerization initiator to actinic rays, inhibiting oxygen from inhibiting polymerization of the polymerizable compound, and the like.

Examples of such a hydrogen-supplying compound include amines (for example, compounds described in "Journal of Polymer society" of M.R. Sander et al, volume 10, page 3173 (1972), Japanese patent publication No. 44-020189, Japanese patent application No. 51-082102, Japanese patent application No. 52-134692, Japanese patent application No. 59-138205, Japanese patent application No. 60-084305, Japanese patent application No. 62-018537, Japanese patent application No. 64-033104, and Research Disclosure No. 33825), and specifically include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.

Further, as another example of the hydrogen-supplying compound, there may be mentioned an amino acid compound (e.g., N-phenylglycine), an organic metal compound (e.g., tributyltin acetate) described in Japanese patent publication No. 48-042965, a hydrogen-supplying substance described in Japanese patent publication No. 55-034414, a sulfur compound (e.g., trithiane) described in Japanese patent application laid-open No. 6-308727, and the like.

From the viewpoint of enhancing the curing rate by the balance between the polymerization growth rate and the chain transfer, the content of these hydrogen-donating compounds is preferably in the range of 0.1 mass% or more and 30 mass% or less, more preferably in the range of 1 mass% or more and 25 mass% or less, and still more preferably in the range of 0.5 mass% or more and 20 mass% or less, with respect to the total mass of the photosensitive layer.

Other ingredients

The photosensitive layer may contain other components than the above components.

Examples of the other component include a heterocyclic compound, a thiol compound, a thermal polymerization inhibitor described in paragraph 0018 of Japanese patent No. 4502784, and other additives described in paragraphs 0058 to 0071 of Japanese patent application laid-open No. 2000-310706.

The photosensitive layer may contain at least 1 seed particle (e.g., metal oxide particle) as another component for the purpose of adjusting the refractive index and the light transmittance.

The metal of the metal oxide particles further contains semimetals such As B, Si, Ge, As, Sb, Te. From the viewpoint of transparency of the cured film, the average primary particle diameter of the particles (e.g., metal oxide particles) is preferably 1nm to 200nm, more preferably 3nm to 80 nm. The average primary particle diameter is calculated by measuring the particle diameters of arbitrary 200 particles using an electron microscope and arithmetically averaging the measurement results. When the shape of the particles is non-spherical, the longest side is regarded as the particle diameter.

The content of the particles is preferably 0 to 35% by mass, more preferably 0 to 10% by mass, even more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, relative to the total mass of the photosensitive layer (that is, the photosensitive layer does not contain particles).

The photosensitive layer may contain a trace amount of a colorant (pigment, dye, etc.) other than the carbon nanotube as another component.

Specifically, the content of the colorant other than the carbon nanotubes in the photosensitive layer is preferably less than 1% by mass, and more preferably less than 0.1% by mass, based on the total mass of the photosensitive layer.

Reflectivity

From the viewpoint of antireflection properties and visibility of display contents when used in a display device, the side of the photosensitive layer having the uneven shape preferably has a normal reflectance of 4% or less and a diffuse reflectance of 0.5% or less, more preferably has a normal reflectance of 1% or less and a diffuse reflectance of 0.5% or less, still more preferably has a normal reflectance of 0.5% or less and a diffuse reflectance of 0.2% or less, and particularly preferably has a normal reflectance of 0.1% or less and a diffuse reflectance of 0.1% or less.

From the viewpoint of antireflection properties and visibility of display contents when used in a display device, the colored layer formed by curing the photosensitive layer preferably has a normal reflectance of 4% or less and a diffuse reflectance of 0.5% or less on the side having the above-described uneven shape, more preferably a normal reflectance of 1% or less and a diffuse reflectance of 0.5% or less, still more preferably a normal reflectance of 0.5% or less and a diffuse reflectance of 0.2% or less, and particularly preferably a normal reflectance of 0.1% or less and a diffuse reflectance of 0.1% or less.

The lower limit values of the normal reflectance and the diffuse reflectance are 0%.

The method for measuring the normal reflectance and diffuse reflectance of the side having the uneven shape of the photosensitive layer or the colored layer in the present invention is as follows: the values of normal reflectance and diffuse reflectance were measured on the surface of the photosensitive layer or the colored layer having the above-described uneven shape using CM-700D manufactured by Konica Minolta, inc. The measurement was performed in a range of 360nm to 740nm on a scale of 10nm, and the value at 550nm was defined as the normal reflectance and diffuse reflectance as representative values of the reflectance.

Color tone

The color tone L value of the side of the photosensitive layer having the uneven shape is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 2 or less, from the viewpoints of antireflection properties and visibility of display contents when used in a display device.

In addition, from the viewpoint of antireflection properties and visibility of display contents when used in a display device, the color tone L value of the colored layer formed by curing the photosensitive layer on the side having the uneven shape is preferably 20 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 2 or less.

The lower limit of the hue L value is 0%.

The method for measuring the hue L value of the side having the uneven shape of the photosensitive layer or the colored layer in the present invention is as follows: the color tone L value was measured on the surface of the photosensitive layer or the colored layer having the uneven shape using CM-700D manufactured by Konica Minolta, inc, in the same manner as the method for measuring the normal reflectance and the diffuse reflectance, and the measurement was performed on a scale of 10nm in a range of 360nm to 740 nm.

Method for Forming photosensitive layer

The method for forming the photosensitive layer is not particularly limited, but the following methods are preferably mentioned: after a photosensitive composition containing the above components is formed by coating and drying on the above protective film, a temporary support having a concavo-convex shape is laminated.

It is preferable to prepare the carbon nanotube dispersion and prepare the photosensitive composition using the carbon nanotube dispersion.

The method of applying the photosensitive composition and the method of drying are not particularly limited, and known methods can be used.

-solvent-

From the viewpoint of forming a layer by coating, the photosensitive composition preferably further contains a solvent.

As the solvent, a solvent generally used can be used without particular limitation.

As the solvent, an organic solvent is preferable.

Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, butyl acetate, propyl acetate, isobutyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, caprolactam, n-propanol, and 2-propanol. The solvent used may contain a mixture of these compounds, i.e., a mixed solvent.

As the solvent, at least 1 solvent selected from the group consisting of butyl acetate and propyl acetate is preferable.

When a solvent is used, the solid content of the photosensitive composition is preferably 5 to 80% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass, based on the total amount of the photosensitive composition.

When a solvent is used, the viscosity (25 ℃) of the photosensitive composition is preferably 1 to 50 mPas, more preferably 2 to 40 mPas, and particularly preferably 3 to 30 mPas, from the viewpoint of coatability.

The viscosity is measured, for example, using VISCOMETER TV-22(TOKI SANGYO co., ltd).

When the photosensitive composition contains a solvent, the surface tension (25 ℃) of the photosensitive composition is preferably 5mN/m to 100mN/m, more preferably 10mN/m to 80mN/m, and particularly preferably 15mN/m to 40mN/m, from the viewpoint of coatability.

The Surface tension is measured, for example, using an Automatic Surface Tensiometer CBVP-Z (Kyowa Interface Science, Inc.).

As the Solvent, Solvent described in paragraphs 0054 and 0055 of specification No. 2005/282073 can be used, and the contents of this specification are incorporated in the present specification.

Further, as the solvent, an organic solvent having a boiling point of 180 to 250 ℃ (high boiling point solvent) may be used as necessary.

< temporary support >

The transfer material of the present invention has a temporary support, and has a concavo-convex shape in at least a part of an interface between the temporary support and the photosensitive layer.

The temporary support is preferably a film, more preferably a resin film.

As the temporary support, a film which has flexibility and does not undergo significant deformation, shrinkage, or expansion under pressure or under pressure and heat can be used.

Examples of such a film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.

The resin film is press-molded as a material to be molded, and a resin film press-mold to which a fine molding pattern of a micrometer or nanometer order is transferred can be formed. The mold to which the molding pattern is transferred is preferably a mold made of silicon or metal. A mold made of silicon is patterned on a silicon substrate or the like by a semiconductor microfabrication technique such as photolithography or etching. The mold made of metal is formed by applying metal plating to the surface of the mold made of silicon by an electroforming (e.g., nickel plating) method and then peeling off the metal plating.

The film used as the temporary support is preferably a film free from deformation such as wrinkles or scratches.

The thickness of the temporary support is not particularly limited, but is preferably 5 to 200 μm, and particularly preferably 10 to 150 μm from the viewpoint of ease of handling and versatility.

The temporary support is preferably a temporary support having an uneven shape, and is preferably a temporary support having a moth-eye structure.

The moth eye (moth eye) structure is an irregular shape having a period (pitch) smaller than 780nm, which is a wavelength of visible light, and the irregular shape can be formed appropriately.

The temporary support having the above-described uneven shape may preferably be a thin film having the above-described uneven shape, and more preferably may be a resin film having the above-described uneven shape.

As the film having the above-described concave-convex shape, a stamper having the above-described concave-convex shape in a thin film shape can be preferably used.

The shape of the irregularities of the temporary support is formed by inverting the shape of the recesses and projections formed on the photosensitive layer, and the preferred form of the irregularities is the same as that of the irregularities.

As the temporary support having the moth-eye structure, a temporary support known as a stamper can be used, and a commercially available product such as a stamper manufactured by SCIVAX corporation can be used.

The transfer material of the present invention is preferably produced by laminating a temporary support having an uneven shape on a photosensitive layer.

The conditions for laminating the temporary support onto the photosensitive layer when the temporary support having the uneven shape is used are not particularly limited, and may be appropriately selected depending on the physical properties of the photosensitive layer, the material of the temporary support, and the like, but the linear pressure at the time of pressing is preferably 5N/cm to 1,000N/cm, more preferably 10N/cm to 500N/cm, and particularly preferably 20N/cm to 200N/cm. The lamination temperature is preferably 0 to 200 ℃, more preferably 25 to 150 ℃, and particularly preferably 50 to 120 ℃.

< protective film >

The transfer material of the present invention may have a protective film on the side opposite to the temporary support when viewed from the photosensitive layer.

Examples of the protective film include a polyethylene terephthalate film, a polypropylene film, a polystyrene film, and a polycarbonate film.

Examples of the protective film include those described in paragraphs 0083 to 0087 and 0093 of jp 2006 and 259138 a.

The thickness of the protective film is not particularly limited, but is preferably 5 μm to 200 μm, and particularly preferably 10 μm to 150 μm from the viewpoint of ease of handling and versatility.

The transfer material of the present invention may have the support and a layer (other layer) other than the photosensitive layer.

Examples of the other layer include layers known as transfer materials.

Further, an adhesive layer may be provided between the protective film and the photosensitive layer.

As the material of the adhesive layer, a known adhesive or bonding agent can be used.

(laminated body)

Embodiment 1 of the laminate of the present invention has a layer obtained by transferring the photosensitive layer of the transfer material of the present invention onto a support.

Embodiment 2 of the laminate of the present invention has a colored layer formed by transferring and curing the photosensitive layer of the transfer material of the present invention on a support.

The layer to which the photosensitive layer is transferred in embodiment 1 of the laminate of the present invention is preferably a layer that can be patterned.

In embodiment 2 of the laminate of the present invention, the colored layer formed by transferring and curing the photosensitive layer is preferably a patterned layer.

< front part of LED display >

The laminate of the present invention can be used as a front part of an LED (light emitting diode) display, and particularly can be preferably used as a front part of a micro LED (μ -LED) display.

The size (maximum diameter) of the LEDs in the above-described micro LED display is preferably less than 100 μm.

The front member is a member provided on the display side of the LED display.

Further, the front member of the LED display of the present invention is preferably a front member for removing stray light of the LED display.

When the laminate of the present invention is used as a front part of an LED display, both regular reflection and diffused reflection can be suppressed, and therefore, the LED display including the front part of the LED display using the laminate of the present invention can display a clear black image with little reflection and stray light, and has excellent visibility of display contents.

Examples of the front member of the LED display include those used in the LED displays described in paragraphs 0032 to 0038 of jp 2014-209198, in which the colored layer in the present invention corresponds to the light transmission suppression layer 31 and the support corresponds to the 2 nd substrate 12. Further, an LED display described in paragraphs 0039 to 0042 of jp 2014-209198 a is also exemplified, and in this example, the colored layer in the present invention corresponds to the light-impermeable layer 34, and the support corresponds to the light-permeable portion 35.

< support >

The laminate of the present invention has a support.

The support is not particularly limited, and a known support can be used.

Examples of the support include a resin film, a glass substrate, a ceramic substrate, a metal substrate, a semiconductor substrate, and a substrate provided with an LED element.

If necessary, the support may have a structure known in display devices such as LED displays, such as wiring, an insulating layer, a light transmission suppressing layer, a light non-transmitting layer, and a protective layer.

The thickness of the support is not particularly limited and can be appropriately set as needed.

< other layers and structures >

The laminate of the present invention may have the support, and a layer obtained by transferring the photosensitive layer or a layer and a structure (other layer and structure) other than the colored layer.

Examples of the other layer and structure include a display device such as an LED display, and a layer and structure known as a transfer material.

The layer to which the photosensitive layer is transferred or the colored layer (preferably, the colored layer) may have a protective layer for protecting the uneven shape.

The material of the protective layer is not particularly limited, and a known resin or a known cured resin may be used.

(method of producing laminate)

The method for producing the laminate of the present invention is not particularly limited except for the method using the transfer material of the present invention, but preferably includes a step of forming a photosensitive layer on a support using the transfer material of the present invention (also referred to as a "transfer step") and a step of patterning the photosensitive layer (also referred to as a "patterning step").

< transfer step >

The method for producing a laminate of the present invention preferably includes a step of forming a photosensitive layer on a support using the transfer material of the present invention (transfer step).

In the transfer step, the photosensitive layer in the transfer material of the present invention is preferably laminated on the support from the side opposite to the side having the temporary support.

When the transfer material to be used has a protective film, the lamination is preferably performed after the protective film is peeled off.

The lamination (transfer of the photosensitive layer) can be performed using a known laminator such as a vacuum laminator or an automatic cutting laminator.

As the lamination conditions, usual conditions can be applied.

The lamination temperature is not particularly limited, but is preferably 80 to 150 ℃, more preferably 90 to 150 ℃, and particularly preferably 100 to 150 ℃.

In the case of using a laminator provided with a rubber roller, the lamination temperature refers to the rubber roller temperature.

The substrate temperature at the time of lamination is not particularly limited. The substrate temperature during lamination is 10 to 150 ℃, preferably 20 to 150 ℃, and more preferably 30 to 150 ℃. When a resin substrate is used as the substrate, the substrate temperature at the time of lamination is preferably 10 to 80 ℃, more preferably 20 to 60 ℃, and particularly preferably 30 to 50 ℃.

The linear pressure at the time of lamination is not particularly limited, but is preferably 0.5N/cm to 20N/cm, more preferably 1N/cm to 10N/cm, and particularly preferably 1N/cm to 5N/cm.

The conveying speed (stacking speed) at the time of stacking is preferably 0.5 m/min to 5 m/min, and more preferably 1.5 m/min to 3 m/min.

< step of patterning >

The method for producing a laminate of the present invention preferably includes a step of patterning the photosensitive layer (patterning step).

The step of patterning is not particularly limited, and a known patterning method can be used, but preferably includes a step of pattern-exposing the photosensitive layer (also referred to as a "pattern exposure step") and a step of developing the photosensitive layer subjected to pattern exposure (also referred to as a "development step").

Pattern Exposure Process

The pattern exposure step is a step of pattern-exposing the photosensitive layer.

Here, the pattern exposure refers to exposure in a pattern-like manner, that is, in a manner in which an exposed portion and a non-exposed portion are present.

For example, in the case where the photosensitive layer is a negative photosensitive layer (for example, the photosensitive layer is a layer containing an ethylenically unsaturated compound and a photopolymerization initiator), an exposed portion at the time of pattern exposure is cured in the photosensitive layer to form a final cured film. In the photosensitive layer, the non-exposed portion is not cured at the time of pattern exposure, and is removed (dissolved) by a developing solution in the subsequent developing step. The non-exposed portion can form an opening of the cured film after the developing step.

The pattern exposure may be exposure through a mask, or may be digital exposure using a laser or the like.

The light source for pattern exposure can be appropriately selected and used as long as it can irradiate light (for example, 365nm or 405nm) in a wavelength region capable of curing the photosensitive layer. Examples of the light source include various lasers, Light Emitting Diodes (LEDs), ultra-high pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5mJ/cm²～2,000mJ/cm²More preferably 10mJ/cm²～1,000mJ/cm²。

In the case where the photosensitive layer is formed on the support using a transfer film, pattern exposure may be performed after the temporary support is peeled, or the temporary support may be peeled after exposure is performed before the temporary support is peeled.

(developing Process)

The developing step is a step of developing the photosensitive layer exposed to the pattern (i.e., dissolving the unexposed portion in a developing solution when the pattern is exposed).

The developer used for development is not particularly limited, and a known developer such as the developer described in japanese patent application laid-open No. 5-072724 can be used.

As the developer, an alkaline aqueous solution is preferably used.

Examples of the basic compound that can be contained in the basic aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide), and the like.

The pH of the alkaline aqueous solution at 25 ℃ is preferably 8 to 13, more preferably 9 to 12, and particularly preferably 10 to 12.

The content of the basic compound in the basic aqueous solution is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total amount of the basic aqueous solution.

The developer may contain an organic solvent miscible with water.

Examples of the organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-N-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, epsilon-caprolactone, gamma-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactam, and N-methylpyrrolidone.

The concentration of the organic solvent is preferably 0.1 to 30% by mass.

The developer may contain a known surfactant. The concentration of the surfactant is preferably 0.01 to 10% by mass.

Examples of the development method include spin-on immersion development, shower and spin development, and immersion development.

In the case of performing the shower development, the unexposed portion of the photosensitive layer can be removed by spraying a developing solution in a shower shape to the photosensitive layer after the pattern exposure.

After development, it is preferable to remove the development residue by spraying a cleaning agent or the like with a shower while wiping with a brush or the like.

The solution temperature of the developer is preferably 20 to 40 ℃.

The developing step may include a step of performing the above-described development and a step of performing a heat treatment (hereinafter, also referred to as "post-baking") on the cured film obtained by the above-described development.

When the substrate is a resin substrate, the temperature of the post-baking is preferably 100 to 160 ℃, more preferably 130 to 160 ℃.

By this post baking, the resistance value of the transparent electrode pattern can also be adjusted.

The developing step may include a step of performing the above-described development and a step of exposing the cured film (colored layer) obtained by the above-described development (hereinafter, also referred to as "post-exposure").

When the developing step includes a post-exposure step and a post-baking step, the post-exposure and the post-baking are preferably performed in this order.

For pattern exposure, development, and the like, for example, reference may be made to the descriptions in paragraphs 0035 to 0051 of japanese patent application laid-open No. 2006-023696.

The method for producing a laminate of the present invention may include other steps than the above-described steps. As the other step, a step (for example, a cleaning step or the like) which may be provided in a general photolithography step can be applied without particular limitation.

Examples

The present invention will be described in more detail with reference to examples. Materials, amounts used, ratios, contents of processes, processing procedures, and the like shown in the following examples can be appropriately modified within a range not departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

< preparation of Black Dispersion K1 >

2.0 parts by mass of carbon nanotubes (CNT, single layer, average fiber diameter 20nm), 6.0 parts by mass of a styrene-acrylic polymer (S.C. Johnson. Polymer Ltd., Joncryl683), and 92.0 parts by mass of butyl acetate were charged in a glass bottle, and dispersed using a paint conditioner for 1 hour with zirconia beads 0.5 mm. phi as a medium, to obtain a black dispersion K1.

Using the black dispersion K1, the following coating liquids were prepared as coating liquids for forming a black layer.

< preparation of Black layer coating liquid 1>

Black dispersion K1: 20 parts by mass

Propyl acetate: 7.37 parts by mass

Dipentaerythritol hexaacrylate (Nippon Kayaku co., ltd.): 5.63 parts by mass

Benzyl methacrylate/methacrylic acid random copolymer (molar ratio 70/30, weight average molecular weight 5,000)45 mass% propylene glycol monomethyl ether acetate solution: 18.19 parts by mass

IRGACURE OXE-02 (manufactured by BASF corporation): 0.55 part by mass

Megaface F551 (manufactured by DIC Corporation): 0.09 part by mass

< preparation of Black film >

On a polyethylene terephthalate film temporary support (protective film 1) having a thickness of 75 μm, a black layer coating solution composed of the black layer coating solution 1 was applied using a slit nozzle and dried. A black resin layer (photosensitive layer) having a dry film thickness of 8.0 μm was thus provided on the temporary support, and finally a protective film 2 (polypropylene film having a thickness of 12 μm) was pressure-bonded as a protective release layer. A transfer material in which the temporary support, the photosensitive layer, and the protective release layer were integrated was prepared in this manner, and the sample name was designated as transfer material black 1.

(example 1)

< preparation of transfer Material >

A substrate with a black pattern was produced by the following procedure using the transfer material black 1.

The surface of the black layer exposed by peeling the protective film 2 was superimposed on a stamper FMES250/300 (manufactured by SCIVAX corporation), and bonded using a laminator lamiii type (manufactured by hitachi corporation) under a pressure and heat condition of 100N/cm linear pressure, 100 ℃ upper roll and 100 ℃ lower roll at a conveying speed of 4 m/min, to produce a transfer material 1 (transfer material of the present invention).

< Pattern formation >

The obtained transfer material 1 was cut into a shape of 10cm × 10cm, and exposed to an exposure dose of i-ray 500mJ/cm from the stamper side with an exposure dose of i-ray through an exposure mask having a light-shielding pattern (diameter 3mm) in the shape of a hole using a proximity type exposure machine (manufactured by Hitachi high-tech electronics engineering Co., Ltd.) having an ultra-high pressure mercury lamp²After proximity exposure with a mask gap of 100 μm, the stamper was peeled off.

Subsequently, the black layer of the laminate from which the stamper was peeled was developed for 40 seconds using a1 mass% aqueous solution of sodium carbonate as a developer (liquid temperature: 32 ℃ C.). After the development, pure water spray was sprayed for 120 seconds to clean the substrate by pure water spray, and air was blown to obtain a black pattern image.

(examples 2 to 12)

A black pattern image was obtained in the same manner as in example 1 except that the height of the formed protrusions, the average pitch of the protrusions, the content of the carbon nanotubes, the average fiber diameter of the carbon nanotubes, and the average thickness of the photosensitive layer were changed as shown in table 1.

(example 13)

A black pattern image was obtained in the same manner as in example 1, except that the carbon nanotubes (single-layer, average fiber diameter 20nm) were changed to carbon nanotubes (multilayer, average fiber diameter 10 nm). The multilayered carbon nanotube is produced by the method described in paragraphs 0076 to 0078 of international publication No. 16/084697.

(example 14)

A black pattern image was obtained in the same manner as in example 1 except that dipentaerythritol hexaacrylate in the black layer coating liquid was changed to pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd., A-TMMT manufactured by Ltd.).

(example 15)

A black pattern image was obtained in the same manner as in example 1 except that dipentaerythritol hexaacrylate in the black layer coating liquid was changed to trimethylolpropane triacrylate (Shin-Nakamura Chemical co., Ltd, a-TMPT).

(example 16)

A black pattern image was obtained in the same manner as in example 1, except that the benzyl methacrylate/methacrylic acid random copolymer in the black layer coating liquid was changed to the following polymer D as a solid component.

< preparation of a 36.3% by mass solution of the solid content of Polymer D >

As the binder polymer, a 36.3 mass% solution (solvent: propylene glycol monomethyl ether acetate) of polymer D having the following structure in solid content was used. In the polymer D, the numerical value on the lower right of each structural unit represents the content ratio (mol%) of each structural unit.

A 36.3 mass% solid content solution of the polymer D was prepared by the following polymerization step and addition step.

[ chemical formula 8]

Polymerization process-

Into a2,000 mL flask, 60g of propylene glycol monomethyl ether acetate (manufactured by SANWA KAGAKU SANGYO co., ltd., trade name PGM-Ac) and 240g of propylene glycol monomethyl ether (manufactured by SANWA KAGAKU SANGYO co., 1td., trade name PGM) were introduced. The resultant liquid was heated to 90 ℃ while being stirred at a stirring speed of 250rpm (revolutions per minute; the same applies hereinafter).

As the preparation of the dropping solution (1), 107.1g of methacrylic acid (MITSUBISHI RAYON CO., LTD. manufactured, trade name Acryester M), 5.46g of methyl methacrylate (MITSUBISHI GAS CHEMICAL COMPANY, INC. manufactured, trade name MMA) and 231.42g of cyclohexyl methacrylate (MITSUBISHI GAS CHEMICAL COMPANY, INC. manufactured, trade name CHMA) were mixed and diluted with PGM-Ac 60g to obtain the dropping solution (1).

As preparation of dropping solution (2), 9.637g of dimethyl 2, 2' -azobis (2-methylpropionate) (polymerization initiator, product name V-601 manufactured by Wako Pure Chemical Corporation) was dissolved with 136.56g of PGM-Ac to obtain dropping solution (2).

The dropping solution (1) and the dropping solution (2) were simultaneously dropped into the above-mentioned 2,000mL flask (specifically, a2,000 mL flask containing a liquid heated to 90 ℃ C.) over 3 hours. Next, the container of the dropping solution (1) was washed with PGM-Ac 12g, and the washing solution was dropped into the above 2000mL flask. Next, the container of the dropping solution (2) was washed with PGM-Ac 6g, and the washing solution was dropped into the above-mentioned 2,000mL flask. When these were added dropwise, the reaction mixture in the 2,000mL flask was stirred at a stirring speed of 250rpm while being kept at 90 ℃. Further, as a post-reaction, stirring was carried out at 90 ℃ for 1 hour.

As an additional initiator, 2.401g of V-601 was added to the reaction mixture after the post-reaction for the 1 st addition. Further, the vessel of V-601 was cleaned with PGM-Ac 6g, and the cleaning solution was introduced into the reaction solution. Thereafter, the mixture was stirred at 90 ℃ for 1 hour.

Next, 2.401g of V-601 was added to the reaction mixture as an additional 2 nd addition of the initiator. Further, the vessel of V-601 was cleaned with PGM-Ac 6g, and the cleaning solution was introduced into the reaction solution. Thereafter, the mixture was stirred at 90 ℃ for 1 hour.

Next, 2.401g of V-601 was added to the reaction mixture as an additional initiator addition 3 times. Further, the vessel of V-601 was cleaned with PGM-Ac 6g, and the cleaning solution was introduced into the reaction solution. Thereafter, the mixture was stirred at 90 ℃ for 3 hours.

An addition process-

After stirring at 90 ℃ for 3 hours, 178.66g of PGM-Ac was introduced into the reaction mixture. Next, 1.8g of tetraethylammonium bromide (manufactured by Wako Pure Chemical Corporation) and 0.8g of hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Corporation) were added to the reaction solution. Further, the respective containers were cleaned with PGM-Ac 6g, and the cleaning solution was introduced into the reaction solution. Thereafter, the temperature of the reaction solution was raised to 100 ℃.

Then, 76.03G of glycidyl methacrylate (manufactured by NOF CORPORATION, trade name, Blemmer G) was added dropwise to the reaction solution over 1 hour. The vessel of the Blemmer G was cleaned with PGM-Ac 6G, and the cleaning solution was introduced into the reaction solution. Thereafter, as an addition reaction, stirring was carried out at 100 ℃ for 6 hours.

Subsequently, the reaction solution was cooled and filtered through a mesh filter for garbage disposal (100 mesh), whereby 1,158g of a solution of the polymer D (solid content concentration 36.3 mass%) was obtained. The resulting polymer D had a weight average molecular weight of 27,000, a number average molecular weight of 15,000 and an acid value of 95 mgKOH/g.

(example 17)

A black pattern image was obtained in the same manner as in example 1 except that dipentaerythritol hexaacrylate in the black layer coating liquid was changed to VISCOAT #802 (a mixture of tripentaerythritol acrylate, mono-and dipentaerythritol acrylate, and polypentaerythritol acrylate, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY ltd.).

(example 18)

After the stamper was bonded in example 1, the temporary support (protective film 1) was peeled off, and the following optically clear adhesive sheet (OCA) was bonded, and then, exposure, peeling, and development were performed in the same manner as in example 1, thereby obtaining a black pattern image.

Transparent adhesive sheet for optical use: CLEARIT JHA200 manufactured by Mitsubishi Chemical corporation, film thickness 200 μm, UV curable type

Comparative example 1

A black pattern image was obtained in the same manner as in example 1 except that the carbon nanotubes were changed to carbon black (CB, average particle diameter 20nm, MA600 manufactured by Mitsubishi Chemical corporation).

Comparative example 2

A black pattern image was obtained in the same manner as in comparative example 1 except that the stamper FMES250/300 was not used, exposure was directly performed without peeling the protective film, and development was performed with peeling the protective film.

Comparative example 3

A black pattern image was obtained in the same manner as in example 1 except that the stamper FMES250/300 was not used, exposure was directly performed without peeling the protective film, and development was performed with peeling the protective film.

< evaluation >

Evaluation of Normal reflectance (SCI reflectance) and diffused reflectance (SCE reflectance) -

Values of normal reflectance and diffuse reflectance were measured from the surface reflectance of the black pattern-containing side of the obtained black pattern image using CM-700D manufactured by Konica Minolta, inc. The measurement was performed in a scale of 10nm in a range of 360nm to 740nm, and the reflectance was judged as a representative value at a value of 550nm, and evaluated based on the following evaluation criteria.

A: the normal reflectance and the diffuse reflectance are both 0.1% or less

B: normal reflectance is greater than 0.1% and 2.0% or less, or diffuse reflectance is 0.2 or less, or both

C: normal reflectance is greater than 2.0% and less than 4.0%, or diffuse reflectance is 0.2% or less, or both

D: normal reflectance of 4.0% or more, or diffuse reflectance of more than 0.2%, or both

Mapping visual evaluation-

In fluorescent lamps (ceiling lighting (fluorescent lamp 2,500 cd/m)²) In the examples and comparative examples, the substrate on which the black pattern image obtained in each example and comparative example was formed was placed, and visual evaluation was performed at 2 angles of 5 degrees and 45 degrees with respect to the bottom surface of the substrate from the left, right, and up and down directions with respect to the substrate, and the intensity of the fluorescent lamp reflected in the black pattern image was evaluatedThe sensory evaluation was carried out.

A: almost end-mapped

B: when carefully observed, the shadow is reflected

C: latent image

D: can clearly confirm from any angle

Determination of the lightness L value

L was calculated by using Konica Minolta, CM-700D manufactured by Inc. in addition to the above-mentioned reflectance measurement^*The value (D65).

[ Table 1]

The values in the column of the average fiber diameter of the carbon nanotubes in comparative example 1 and comparative example 2 in table 1 are the values of the average particle diameter of carbon black.

As is clear from the results shown in table 1, the diffuse reflectance and the normal reflectance of the black members formed from the transfer materials of examples 1 to 18 were lower than those of the black members formed from the transfer materials of the comparative examples.

The disclosure of japanese patent application No. 2018-183513, applied at 28.9.2018, is incorporated by reference in its entirety into this specification.

All documents, patent applications, and technical standards described in the present specification may be incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard were specifically and individually described to be incorporated by reference.