JP2003177522A - Image forming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming material having no unevenness in coating, a smooth coated surface state, a uniform layer thickness, no irregular color, no repellency, no pinhole and excellent adhesiveness to a glass substrate. <P>SOLUTION: In the image forming material obtained by disposing at least an alkali-soluble thermoplastic resin layer and a photosensitive resin layer in this order on a support, a copolymer surfactant containing a specified fluorine-containing monomer is contained in at least one of the thermoplastic resin layer and the photosensitive resin layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming material which can be advantageously used for image formation by transfer such as production of color filters used for production of color liquid crystal displays.

[0002]

2. Description of the Related Art An image forming material for transferring a photosensitive resin layer provided on a support to form a photosensitive resin layer on a substrate which is an object to be transferred is, for example, JP-B-56-40824.
It is known from the issue. This image forming material is used for producing printed wiring, intaglio relief printing plate, name plate, multicolor test printing sample, offset printing plate or screen printing stencil. The above-mentioned image forming material usually comprises a support, an intermediate layer (separation layer) or an intermediate layer and an alkali-soluble thermoplastic resin layer and a photosensitive resin layer. An image can be formed on the substrate by bringing the photosensitive resin layer surface of the material into close contact with the substrate that is the transfer target, peeling off only the support, exposing through the intermediate layer, and further developing.
In this case, the intermediate layer plays a role of blocking oxygen and has an advantage for exposure in air, but the film thickness is 0.5 to 5
Since it is as thin as about μm, there is no particular problem in terms of resolution. The alkali-soluble thermoplastic resin layer can absorb the unevenness of the base (that is, the unevenness due to the already formed image).

For example, color filters used in color liquid crystal displays are generally R, G, B (red,
It has a basic structure in which each pixel of green and blue and a black matrix (K) is formed in the gap between them for the purpose of improving display contrast. High smoothness is required for the surface of these R, G, B, each pixel and K in the color filter. That is, when the photosensitive resin layer is transferred onto the surface of the color filter substrate by using the above image forming material to form an image, the smoothness of the photosensitive resin layer is not good (that is, there is unevenness in film thickness). In this case, color unevenness of pixels occurs. When a color liquid crystal display is produced using a color filter having such color unevenness, the pixels obtained on the color liquid crystal display also do not cause color unevenness, so that application unevenness and repelling do not occur during application. Need to be applied.

Similarly, in the lower alkali-soluble thermoplastic resin layer as well, from the viewpoint of affecting the coating property of the photosensitive resin layer, it is essential that smoothness is ensured to ensure uniform exposure of the thermoplastic resin layer. Therefore, it is necessary to prevent uneven coating and cissing during coating.

To address such problems, Japanese Patent Publication No. 8-363
Japanese Patent Laid-Open Publication No. 0-202 proposes to add a fluorine-based surfactant to the coating solution when the photosensitive resin layer is formed by coating. Fluorine-based surfactants with 3 to 3 carbon atoms
An acrylate or a methacrylate having a fluoroaliphatic group having 20 and containing 40% by mass or more of a fluorine atom, and a hydrogen atom bonded to at least three terminal carbon atoms is fluorine-substituted; poly (oxyalkylene) ) Copolymers with acrylates or poly (oxyalkylene) methacrylates, with 40 to 70 acrylate or methacrylate units having fluoroaliphatic groups in the copolymer.
A polymer contained in the range of mass% is used. Fluorine-based surfactants used in many examples include
As the oxyalkylene of poly (oxyalkylene) (meth) acrylate, those having oxyethylene, oxytriethylene or oxytetramethylene are used, and those having a mass average molecular weight of about 15,000 are mainly used.

Some of the fluorine-based surfactants used in the examples of Japanese Patent Publication No. 8-3630 can smooth the surface of the photosensitive resin layer, but the adhesiveness to the substrate is still low. Insufficient, especially when transferred to a glass substrate or a substrate provided with a semiconductor, the adhesion to the substrate is not sufficient.

[0007]

An object of the present invention is to provide an image which has no coating unevenness, a smooth coating surface condition, a uniform layer thickness, no color unevenness, cissing and pinholes, and excellent glass substrate adhesiveness. To provide a forming material.

[0008]

[Means for Solving the Problems] Means for solving the above problems are as follows. (1) In an image-forming material comprising a support and at least a coating layer comprising an alkali-soluble thermoplastic resin layer and a photosensitive resin layer provided in this order, the thermoplastic resin layer and the photosensitive resin layer An image forming material comprising at least one of a copolymer containing a monomer represented by the general formula (a) and a monomer represented by the general formula (b).

[0009]

[Chemical 2]

(In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ₁ represents a single bond or a linking group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom. n is an integer of 1 to 20, m is an integer of 2 to 14, l is an integer of 0 to 10, p is an integer of 2 to 10, and q is an integer of 1 to 30. (2) The image forming material as described in (1) above, wherein at least the photosensitive resin layer of the coating layer is provided by spin coating.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The image forming material used in the present invention is
Monomers represented by the general formula (a) and the general formula (b) in at least one of an alkali-soluble thermoplastic resin layer (hereinafter, also simply referred to as a thermoplastic resin layer) and a photosensitive resin layer that constitute the coating layer. Containing a copolymer containing. Since the above-mentioned copolymer has a surface active function, it is also called a surfactant for the present invention. The image forming material of the present invention is configured such that at least the photosensitive resin layer is transferred to the surface of an arbitrary member. The surface of the arbitrary member is also referred to as a base surface. In the image forming material of the present invention, the surfactant for the present invention is added to the thermoplastic resin layer and / or
Or by including in the photosensitive resin layer, the coating liquid performance of each of the thermoplastic resin layer and / or the photosensitive resin layer is improved,
It is possible to provide an image-forming material having no coating unevenness, a smooth coating surface state, a uniform layer thickness, no color unevenness, no foaming, excellent defoaming properties, and excellent base surface adhesiveness. In particular,
Excellent adhesion to a glass substrate or a substrate having a semiconductor as a base. In the present invention, the photosensitive resin layer is used for image formation, and the image also includes a colorless transparent image.
When obtaining a color image, a colorant is contained.

The surfactant for use in the present invention will be described below. The monomer represented by the general formula (a) of the surfactant for use in the present invention is referred to as a monomer (a), and the monomer represented by the general formula (b) is referred to as a monomer (b). The monomer (a) will be described. C _m F _{2m + 1} may be linear or branched. m shows the integer of 2-14, Preferably it is the integer of 4-12. The content of C _m F _{2m + 1} is 2 with respect to the monomer (a).
0 to 70 mass% is preferable, and 40 to 60 mass% is particularly preferable. R ₀₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ₁ represents a single bond or a linking group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, and preferably a single bond. Examples of the linking group include —SO ₂
NR ₄ — (R ₄ has the same _meaning as R ₀₁ ), —NH—, —O
-, -S- and the like. n shows 1-20, Preferably it shows 2-10. l represents 0 to 10, preferably 0 to 5.

The monomer (b) will be described. R ₀₂ and R ₀₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. More preferably, R ₀₂ is a methyl group and R ₀₃ is a hydrogen atom. p is an integer of 2 to 10, preferably 2 to 3. q is an integer of 1 to 30, preferably 1
~ 25. In particular, the surfactant for use in the present invention is most preferably a mixture of copolymers having a p value of 2 and a p value of 3 as the monomer (b), and the ratio of the former to the mixture is 1 to 20 mass. %, Particularly preferably 1 to 10% by mass. In this case, q is preferably 9 to 22 in both cases.

Weight average molecular weight Mw of the surfactant for use in the present invention
Is preferably 1,000 to 40,000, more preferably 5,000.
˜20,000 is preferable. 100 parts by mass of the surfactant for the present invention may be composed of 5 to 80 parts by mass of the monomer (a), 0.1 to 50 parts by mass of the monomer (b), and the remaining parts by mass of other optional monomers. More preferably, the monomer (a) is 10 to 60 parts by mass, the monomer (b) is 10 to 40 parts by mass, and the other optional monomers are preferably the remaining parts by mass. As the copolymerizable monomer other than the monomers (a) and (b),
The following monomers (c) are preferred.

[0015]

[Chemical 3]

The monomer (c) will be described. R ₀₄ and R ₀₅ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ₀₄ is a hydrogen atom or 1 to 1 carbon atoms
Alkyl groups of 3 are preferred. R ₀₅ is preferably an alkyl group having 1 to 3 carbon atoms. Copolymerizable monomers other than the above include styrene, vinyltoluene, α-methylstyrene, 2-methylstyrene, chlorostyrene, vinylbenzoic acid, sodium vinylbenzene sulfonate, styrene such as aminostyrene, and derivatives thereof, and substitution products. , Dienes such as butadiene and isoprene, acrylonitrile, vinyl ethers, maleic acid and maleic acid esters,
Examples thereof include maleic anhydride, cinnamic acid, vinyl chloride and vinyl-based monomers such as vinyl acetate. The surfactant for use in the present invention is a copolymer of the monomer (a), the monomer (b), etc., but the monomer sequence is not particularly limited and may be random or regular, for example, block or graft. The monomers (a) contained in one molecule of the surfactant for use in the present invention may have the same structure or different structures within the above defined range. This is
The same applies to the monomer (b) and further to the monomer (c). Further, the surfactant for use in the present invention has a molecular structure and / or
Alternatively, two or more having different monomer compositions can be mixed and used.

The content of the surfactant for use in the present invention is preferably 0.01 to 10% by mass, more preferably 0.1 to 6% by mass, based on the total solid content of the thermoplastic resin layer or the photosensitive resin layer. Is preferred. The surfactant for use in the present invention is more effective when used in both the thermoplastic resin layer and the photosensitive resin layer.

The coating layer constitution of the image forming material of the present invention is not particularly limited as long as it has at least the thermoplastic resin layer and the photosensitive resin layer, but will be described in detail with reference to the drawings. The layer structure of the image forming material of the present invention is not limited to the following specific examples. In the image-forming material shown in FIG. 1, an alkali-soluble thermoplastic resin layer 2, an oxygen barrier layer 3, and a photosensitive resin layer 4 are sequentially formed on a support 1. At least one of the alkali-soluble thermoplastic resin layer 2 and the photosensitive resin layer 4 contains the surfactant of the present invention. The support is preferably composed of a flexible material that has good releasability from the alkali-soluble thermoplastic resin layer, is chemically and thermally stable, and is flexible. Specifically, a thin sheet of Teflon (registered trademark), polyethylene terephthalate (PET), polycarbonate, polyethylene, polypropylene or the like or a laminate thereof is preferable.

In order to ensure good releasability between the support and the thermoplastic resin layer, surface treatment such as glow discharge is not performed, and an undercoat layer such as gelatin is not provided. Is. The thickness of the support is appropriately 5 to 300 μm,
20 to 150 μm is preferable.

The alkali-soluble thermoplastic resin layer plays a role as a cushioning material so as to absorb irregularities (including irregularities due to an image already formed) on the surface of the base. It is preferable that it has a property of being deformable according to the unevenness.

The resin contained in the alkali-soluble thermoplastic resin layer includes saponified products of ethylene and an acrylic ester copolymer, saponified products of styrene and a (meth) acrylic ester copolymer, and vinyltoluene. Saponification products of (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, and saponification products of (meth) acrylic acid ester copolymers of butyl (meth) acrylate and vinyl acetate, etc. At least one selected from the above is preferable, but an organic polymer according to "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Board, issued October 25, 1968) Of these, those soluble in an alkaline aqueous solution can be used. Further, among these thermoplastic resins, those having a softening point of 80 ° C. or lower are preferable. In the present specification, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.

Among these resins, the mass average molecular weight is in the range of 50,000 to 500,000 (Tg = 0 to 140 ° C.), and more preferably the mass average molecular weight is 60,000 to 200,000 (Tg = 30 to 110).
C) can be selected and used in the range. Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, and JP-B-58-12577.
JP-B-54-25957, JP-A-61-134756
Japanese Patent Publication No. 59-144615, JP-A-54-9272.
3, JP-A-54-99418, JP-A-54-137.
085, JP-A-57-20732, and JP-A-58-9.
3046, JP-A-59-97135, JP-A-60-
159743, OLS3504254, JP-A-60
-247638, JP-A-60-208748, JP-A-60-214354, and JP-A-60-230135.
JP-A-60-258539 and JP-A-61-169.
829, JP-A-61-213213, and JP-A-63-132.
147159, JP-A-63-213837, JP-A-63-266448, JP-A-64-55551, JP-A-64-155550, JP-A-2-191955,
JP-A-2-199403 and JP-A-2-199404
Japanese Patent Application Laid-Open No. 2-208602, Japanese Patent Application No. 4139653.
Examples thereof include resins soluble in an alkaline aqueous solution described in each of the specifications. Particularly preferred is the methacrylic acid / 2-ethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.

Further, among the above-mentioned various resins, the mass average molecular weight is preferably 3,000 to 30,000 (Tg = 30 to 170).
C) range, and more preferably a mass average molecular weight of 4,000 to 2
It can be selected and used in the range of 10,000 (Tg = 60 to 140 ° C.). Preferred specific examples can be selected from those described in the above patent specifications, and particularly preferred are JP-B-55-38961 and JP-A 5-2.
The styrene / (meth) acrylic acid copolymer described in No. 41340 is mentioned.

In order to adjust the adhesive force between these organic polymer substances and the adhesive force with the support, various plasticizers,
It is possible to add various polymers, supercooling substances, adhesion improvers or surfactants, release agents and the like. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono ( Addition reaction product with (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) ac Addition reaction products of rate, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate. The amount of the plasticizer in the alkali-soluble thermoplastic resin layer is generally 200% by mass or less, preferably 20 to 100% by mass, based on the thermoplastic resin. The thickness of the alkali-soluble thermoplastic resin layer is preferably 6 μm or more. If the thickness of the thermoplastic resin is less than 6 μm, it becomes difficult to completely absorb the unevenness of the base surface of 1 μm or more. The upper limit is generally about 100 μm or less, preferably about 50 μm or less, from the viewpoint of developability and production suitability.

The oxygen-blocking layer is a layer having a function of blocking oxygen, and by this, the polymerization of the photosensitive resin layer by exposure can proceed without being disturbed by oxygen even in the air. . Further, since the film thickness is thin (about 0.05 to 5 μm), the resolution is not adversely affected. The material for forming the oxygen barrier layer may be any material that is dispersed or dissolved in water or an aqueous alkali solution and exhibits low oxygen permeability, and known materials can be used. For example, polyvinyl ether / maleic anhydride polymers described in JP-A-46-2121 and JP-B-56-40824, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, Polyvinyl alcohol, polyvinyl pyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, water-soluble salts of any of various starches and the like,
Styrene / maleic acid copolymer, maleate resin,
Further, combinations of two or more of these can be mentioned.

A combination of polyvinyl alcohol and polyvinylpyrrolidone is particularly preferable. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinylpyrrolidone is generally 1 to 75% by mass, preferably 1 to 60% by mass, based on the solid content of the oxygen barrier layer. However, those of 10 to 50 mass% are the most preferable. If this content is less than 1% by mass, sufficient adhesiveness to the photosensitive resin layer cannot be obtained, and if it exceeds 75% by mass, the oxygen blocking ability is lowered. The oxygen barrier layer is very thin and has a thickness of about 0.
It is preferably 1 to 5 μm, and particularly preferably 0.5 to 2 μm. About 0.1
If it is less than μm, oxygen permeability is too high, and if it exceeds about 5 μm, it takes too much time during development or removal of the oxygen barrier layer.

The photosensitive resin layer can be developed with an alkaline aqueous solution or can be developed with an organic solvent, but from the viewpoint of safety and the cost of the developing solution, an alkaline aqueous solution developable layer is preferable. The photosensitive resin may be a negative type in which a portion that receives radiation such as light or an electron beam is cured, or a positive type in which a non-radiation receiving portion is cured.

The positive photosensitive resin may be a novolac resin. For example, the alkali-soluble novolac resin system described in JP-A-7-43899 can be used. Further, a positive photosensitive resin layer described in JP-A-6-148888, that is, an alkali-soluble resin described in the publication, a 1,2-naphthoquinonediazidesulfonic acid ester as a photosensitizer, and a thermosetting agent described in the publication. A photosensitive resin layer containing a mixture can be used. In addition, JP-A-5-26
The composition described in Japanese Patent No. 2850 can also be used.

As the negative photosensitive resin, a photosensitive resin containing a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition containing an azide compound and a binder, and a cinnamic acid photosensitive resin composition. Etc. Among them, particularly preferred is a photosensitive resin containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. The photosensitive resin layer is provided with JP-A-11-1336.
"Polymerizable compound B" and "Polymerization initiator C" described in JP-A-00
"Surfactant", "adhesion aid", and other compositions can be used. For example, a negative type photosensitive resin that can be developed in an alkaline aqueous solution may be subjected to addition polymerization by irradiating light with a binder containing a carboxylic acid group as a main component (the above-mentioned alkali-soluble thermoplastic resin). It contains a monamer containing ethylenically unsaturated double bonds and a photoinitiator.

As the alkali-soluble binder, a polymer having a carboxylic acid group in its side chain, for example, JP-A-59 is used.
-44615, Japanese Patent Publication No. 54-34327,
JP-B-58-12577, JP-B-54-2595
7, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include polymers, maleic acid copolymers and partially esterified maleic acid copolymers. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition to these, a polymer having a hydroxyl group and a cyclic acid anhydride added thereto can also be preferably used. In particular, the copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in U.S. Pat. No. 4,139,391 and the multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers are also available. Can be mentioned.

The alkali-soluble binder used in the photosensitive resin layer is selected from those having an acid value in the range of 30 to 400 mgKOH / g and a mass average molecular weight in the range of 1000 to 300,000. In addition to the above, in order to improve various properties, for example, the strength of the cured film, an alkali-insoluble polymer can be added within a range that does not adversely affect the developability and the like. Examples of these polymers include alcohol-soluble nylon and epoxy resins. The alkali-soluble binder is usually 10 to 95% by mass, preferably 20 to 90% by mass, based on the total solid content of the photosensitive resin composition. 10 mass%
If the amount is less than 95% by mass, the tackiness of the photosensitive resin layer is too high.
If it exceeds, the strength and photosensitivity of the layer formed will be poor.

As the photopolymerization initiator, US Pat.
Vicinal polyketaldonyl compounds disclosed in 7660, acyloin ether compounds described in U.S. Pat. No. 2,448,828, U.S. Pat.
Α-hydrocarbon substituted aromatic acyloin compounds described in US Pat. No. 7,225,512, US Pat. No. 3,046,127.
No. 2951758 and polynuclear quinone compounds described in each specification, a combination of a triarylimidazole dimer and p-aminoketone described in US Pat. No. 3,549,367, and JP-B-51-48516. Benzothiazole compound and trihalomethyl-s-triazine compound, trihalomethyl-s-triazine compound described in U.S. Pat. No. 4,239,850, and trihalomethyloxadiazole compound described in U.S. Pat. No. 4,212,976. Etc. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer. In the photosensitive resin layer, the content of the photopolymerization initiator based on the total solid content is generally 0.5 to 20% by mass, preferably 1 to 15% by mass. If it is less than 0.5% by mass, the photosensitivity and the image strength are low, and if it is added in excess of 20% by mass, the effect of improving the performance is not recognized.

Examples of the ethylenically unsaturated double bond-containing monamer which can be addition-polymerized by irradiation with light include compounds having a boiling point of 100 ° C. or higher at normal pressure. For example, monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tri Methylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Trimethylol propane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin. Examples thereof include polyfunctional (meth) acrylates such as those which are (meth) acrylated after the addition reaction of Furthermore, Japanese Examined Japanese Patent Publication No. 48-4170
No. 8, 50-6034, and urethane acrylates disclosed in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191,
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, disclosed in JP-A No. 52-30490 can be mentioned. Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable. These monomers may be used alone or as a mixture of two or more kinds, and the content thereof with respect to the total solid content of the photosensitive resin composition is 5 to 50% by mass.
Is general, and 10-40 mass% is preferable. If it is less than 5% by mass, the photosensitivity and the strength of the image are lowered, and if it exceeds 50% by mass, the tackiness of the photosensitive resin layer becomes excessive, which is not preferable.

The photosensitive resin layer contains at least a pigment or a dye in order to form a colored image on the transferred material. Pigments are generally roughly classified into organic pigments and inorganic pigments, the former having particularly excellent transparency of the coating film, and the latter generally having properties such as excellent hiding properties, so that they can be appropriately selected depending on the application. Good. In addition, metal powder, metal oxide powder, fluorescent pigment, etc. may also be used. Examples of suitable pigments include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The pigments used in the photosensitive resin layer are listed below according to hues, but the pigments are not limited to these. These pigments and dyes may be used alone or in combination.

1) Red pigment C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I. Pigment Red 149,
C. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 18
0, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, CI No. 12085, CI No. 12120,
Organic pigments such as CI No. 12140 and CI No. 12315 2) Green pigment C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, CI No.42053, CI No.42085, CIN
Organic pigments such as o.42095 3) Blue pigment C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 1
5: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 6
4, organic pigments such as CI No. 42052, CI No. 42090

4) Yellow Pigment Pigment Yellow (Pigment Yellow)
12 (C.I. No. 21090) Example) Permanent Yellow (Permanent Yellow) DHG (Clariant Japan KK)
Manufactured by Toyo Ink Mfg. Co., Ltd., Irg
alite Yellow (Irgarite yellow)
LCT (Ciba Specialty Chemicals Co., Ltd.)
), SYMLER FAST YELLOW (Shimla Fast Yellow) GTF 219 (Dainippon Ink and Chemicals, Inc.) Pigment Yellow (Pigment Yellow)
13 (CI. No. 21100) Example) Permanent Yellow (Permanent Yellow) GR (manufactured by Clariant Japan Co., Ltd.),
Lionol Yellow (Rionol Yellow)
1313 (manufactured by Toyo Ink Mfg. Co., Ltd.) Pigment Yellow (Pigment Yellow)
14 (CI. No. 21095) Example) Permanent Yellow (Permanent Yellow) G (manufactured by Clariant Japan KK), L
ionol Yellow 1
401-G (manufactured by Toyo Ink Mfg. Co., Ltd.), Seika
Fast Yellow
2270 (manufactured by Dainichiseika Kogyo Co., Ltd.), Symler
Fast Yellow (Shimla First Yellow) 4400 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Yellow (Pigment Yellow)
17 (C.I. No. 21105) Example) Permanent Yellow (Permanent Yellow) GG02 (Clariant Japan KK)
Manufactured by SYMLER FAST Yellow (Shimla First Yellow) 8GF (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Yellow
155 Example) Graphtol Yellow (Graph Thor Yellow) 3GP (Clariant Japan KK) Pigment Yellow (Pigment Yellow)
180 (CI No. 21290) Example) Novoperm Yellow (Novopalm Yellow) P-HG (manufactured by Clariant Japan KK),
PV Fast Yellow (First Yellow)
HG (Clariant Japan KK) Pigment Yellow (Pigment Yellow)
139 (C.I.No. 56298) Example) Novoperm Yellow (Novopalm Yellow) M2R 70 (Clariant Japan KK)
Made)

5) Magenta Pigment Pigment Red 57:
1 (C.I.No. 15850: 1) Example) Graphtol Rubin (Graphtor Rubin) L6B (manufactured by Clariant Japan KK), L
ionol Red 6B-42
90G (Toyo Ink Mfg. Co., Ltd.), Irgalite
Rubine (Irgarite Rubin) 4BL (Ciba Specialty Chemicals Co., Ltd.), Symu
ler Brilliant Carmine 6B-229 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red (Pigment Red) 122
(C.I. No. 73915) Example) Hosterm Pink (Hoster Palm Pink) E (manufactured by Clariant Japan KK), Li
onogen Magenta (Rionogen Magenta)
5790 (manufactured by Toyo Ink Mfg. Co., Ltd.), Fastog
en Super Magenta RH (Dainippon Ink and Chemicals, Inc.)
Made) Pigment Red (Pigment Red) 53:
1 (CI. No. 15585: 1) Example) Permanent Lake Red (Permanent Lake Red) LCY (Clariant Japan Co., Ltd.), SYMLER LAKE RED (Shimla Lake Red) C conc (Dainippon Ink and Chemicals, Inc.) )) Pigment Red 48:
1 (C.I.No. 15865: 1) Example) Lionol Red (Lionol Red) 2B
3300 (manufactured by Toyo Ink Mfg. Co., Ltd.), Symule
r Red (Shimla Red) NRY (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red (Pigment Red) 48:
2 (C.I.No. 15865: 2) Example) Permanent Red (Permanent Red) W2T (manufactured by Clariant Japan KK), Li
onol Red (Rionol Red) LX235
(Manufactured by Toyo Ink Mfg. Co., Ltd.), Symboler Red
(Shimla Red) 3012 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red 48:
3 (C.I.No. 15865: 3) Example) Permanent Red (Permanent Red) 3RL (Clariant Japan KK), Sy
muller Red 2BS (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Red 177
(C.I. No. 65300) Example) Cromophthal Red (Chromophtal red) A2B (manufactured by Ciba Specialty Chemicals Co., Ltd.)

6) Cyan Pigment Pigment Blue 15
(C.I. No. 74160) Example) Lionol Blue (Lionol Blue) 7
027 (manufactured by Toyo Ink Mfg. Co., Ltd.), Fastogen
Blue (Fastgen Blue) BB (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 1 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) A2R (manufactured by Clariant Japan KK),
Fastogen Blue (Fastgen Blue)
5050 (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 2 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) AFL (manufactured by Clariant Japan Co., Ltd.),
Irgalite Blue (Irgalite blue)
BSP (Ciba Specialty Chemicals Co., Ltd.)
Fastogen Blue (Fastgen Blue) GP (manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 3 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) B2G (manufactured by Clariant Japan Co., Ltd.),
Lionol Blue FG73
30 (manufactured by Toyo Ink Mfg. Co., Ltd.), Cromophta
l Blue (chromophthal blue) 4GNP (manufactured by Ciba Specialty Chemicals Co., Ltd.), Fast
gen Blue (Fastgen Blue) FGF
(Manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 4 (C.I. No. 74160) Example) Hosterm Blue (Hoster Palm Blue) BFL (manufactured by Clariant Japan Co., Ltd.),
Cyanine Blue (cyanine blue) 700-
10FG (manufactured by Toyo Ink Mfg. Co., Ltd.), Irgalit
e Blue (Irgalite blue) GLNF (manufactured by Ciba Specialty Chemicals Co., Ltd.), Fast
gen Blue FGS
(Manufactured by Dainippon Ink and Chemicals, Inc.) Pigment Blue (Pigment Blue) 1
5: 6 (C.I. No. 74160) Example) Lionol Blue (Lionol Blue) E
S (manufactured by Toyo Ink Mfg. Co., Ltd.) Pigment Blue (Pigment Blue) 60
(C.I. No. 69800) Example) Hosterperm Blue (Hoster Palm Blue) RL01 (Clariant Japan KK)
Manufactured by Toyo Ink Mfg. Co., Ltd. 7) Black pigment Pigment Black (Pigment Black)
7 (Carbon black CI No. 77266) Example) Mitsubishi carbon black MA100 (manufactured by Mitsubishi Chemical Co., Ltd.), Mitsubishi carbon black # 5 (manufactured by Mitsubishi Chemical Co., Ltd.), Black Pearls (Black Pearls) 430 (Cabot) Co. (Cabot)
Further, as a pigment that can be used in the present invention, "Pigment Handbook, edited by Japan Pigment Technology Association, Seibundo Shinkosha, 198"
9 ”,“ COLOUR INDEX, THE SOCIETY OF
DYES & COLOURIST, THIRD EDITION, 1987 ”, etc. can be referred to to select an appropriate product.

The average particle diameter of the dye or pigment is usually 5 μm or less, preferably 1 μm or less. When making a color filter, 0.5 μm or less is preferable.

The photosensitive resin composition preferably further contains a thermal polymerization inhibitor in addition to the above components. Examples of the thermal polymerization inhibitor include, for example, hydroquinone, p-methoxyphenol, pt-butylcatechol, 2,6-di-t-.
Aromatic hydroxy compounds such as butyl-p-cresol, β-naphthol and pyrogallol, quinones such as benzoquinone and p-toluquinone, naphthylamine, pyridine and p
Amines such as toluidine, phenothiazine, aluminum or ammonium salts of N-nitrosophenylhydroxylamine, chloranil, nitrobenzene,
4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-)
t-butylphenol), 2-mercaptobenzimidazole and the like.

The photosensitive resin composition may further contain known additives such as a plasticizer, a surfactant other than the surfactant for the present invention, an adhesion promoter, a dispersant, a plasticizer, an anti-sagging agent, if necessary. , Leveling agents, defoaming agents, flame retardants, brighteners, solvents and the like can be added. Examples of the adhesion promoter include alkylphenol / formaldehyde novolac resin, polo vinyl ethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene,
Styrene-butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, chlorinated rubber, acrylic resin adhesive, aromatic, aliphatic or alicyclic petroleum resin, silane coupling agent, etc. Can be mentioned.

The layer thickness of the photosensitive resin layer formed from the photosensitive resin composition is preferably in the range of 0.5 to 10 μm, particularly preferably 1 to 5 μm.

The photosensitive resin layer can be obtained, for example, by dispersing a mixture of a colorant and a resin and then mixing other materials.

In the image-forming material of the present invention, for example, an alkali-soluble coating solution for forming a thermoplastic resin layer is applied on the above support and dried to form a thermoplastic resin layer, and the thermoplastic resin is formed. It can be obtained by applying a coating solution for forming a photosensitive resin layer that does not dissolve the thermoplastic resin layer on the layer and drying the coating solution to form the photosensitive resin layer. An oxygen barrier layer may be provided between the thermoplastic resin layer and the photosensitive resin layer. For example, a thermoplastic resin layer is provided on a support, an oxygen barrier layer forming coating solution using a solvent that does not dissolve the thermoplastic resin layer is applied on the support, dried to provide an oxygen barrier layer, and the oxygen barrier layer is further protected. The photosensitive resin layer can be formed by applying a coating solution for forming a photosensitive resin layer on the layer using a solvent that does not dissolve the oxygen blocking layer and drying the solution to form the photosensitive resin layer. Alternatively, a photosensitive resin layer is provided on the covering sheet described below, while a thermoplastic resin layer and an oxygen blocking layer are provided on the support, and these are bonded so that the oxygen blocking layer and the photosensitive resin layer are in contact with each other. Alternatively, or alternatively, the photosensitive resin layer and the oxygen blocking layer are provided on the cover sheet, while the thermoplastic resin layer is provided on the support, and the oxygen blocking layer and the photosensitive resin layer are in contact with each other in the same manner as above. It can be manufactured by laminating in this manner.

For each of the above-mentioned alkali-soluble thermoplastic resin layer, oxygen barrier layer, and photosensitive resin layer, a coating solution for forming each layer (usually, the composition is dissolved in an organic solvent) is provided by a known method. You can For example, spinner, whiler, roller coater, curtain coater, knife coater,
It can be formed by applying each layer forming coating solution using a coating machine such as a wire bar coater or an extruder and drying. In the present invention, at least the photosensitive resin layer is preferably spin-coated with a spinner, and further, all coating layers are preferably spin-coated. The coating conditions are appropriately set depending on the layer thickness, composition, etc., but usually 10 per 1 m ^2.
~ While dropping 700 ml of coating liquid in the center,
A method of spin coating at 1000 rpm can be mentioned. Examples of the solvent used for preparing the coating liquid for forming each layer include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, ethyl lactate, methyl lactate, caprolactam and the like.

A thin covering sheet is preferably provided on the photosensitive resin layer in order to protect it from dirt and damage during storage. The covering sheet may be made of the same or similar material as the support, but it can be easily separated from the photosensitive resin layer. The material used for the covering sheet is preferably, for example, silicone paper, polyolefin sheet, polytetrafluoroethylene sheet, or the like. The thickness of the covering sheet is usually 5 to 100 μm and is 10
-30 μm is preferable.

Usually, when a photosensitive resin layer of an image forming material is bonded onto a permanent support such as a glass substrate and the support is peeled off, an unpleasant electric shock is generated between the charged support (film) and the human body. There is a problem that it may be received or dust adheres to the charged support. For this reason, it is preferable to provide a conductive layer on the support or to perform a treatment for imparting conductivity to the support itself. Further, when the conductive layer is provided on the side opposite to the support (the side having no photosensitive resin layer), it is preferable to provide the hydrophobic polymer layer in order to improve scratch resistance.

The production of a multicolor image sheet such as a color filter using the image forming material of the present invention can be carried out, for example, as follows. The formation of each pixel of red, green and blue is
An image forming material having a red photosensitive resin layer for red pixels is used to transfer the red photosensitive resin layer to the surface of the substrate, and imagewise exposure and development are performed to form red pixels. The same applies to green and blue. And forming each pixel. Red-green,
When arranging the three kinds of pixels of blue, any arrangement such as mosaic type, triangle type, and four-pixel arrangement type may be used.

An image forming material having a black photosensitive resin layer is used to transfer the black photosensitive resin layer onto the surface of the substrate on the upper surface of each pixel of the pixel sheet and the space between the pixels, and back exposure (pixel exposure). (From the side without), develop to form a black matrix. The uncured portion is cured by heating the image sheet (performed for each pixel).

The lamination of the image-forming material of the present invention onto the substrate surface is generally carried out by removing the coating sheet on the photosensitive resin layer of the image-forming material, superposing the image-forming material on the substrate surface, and applying pressure and heat. Done below. For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cutter laminator capable of increasing productivity can be used. After that, the support is peeled off, the photosensitive resin layer is exposed through a predetermined mask, the thermoplastic resin layer and the oxygen barrier layer, and then the unexposed area is removed (development). The light source used for the exposure is
It is selected according to the photosensitivity of the photosensitive resin layer. For example, known ones such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp and an argon laser can be used. JP-A-6-59
As described in Japanese Patent No. 119, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used together.

As the developing solution for the photosensitive resin layer, a dilute aqueous solution of an alkaline substance is used, but a solution containing a small amount of an organic solvent miscible with water may be used. Suitable alkaline substances include alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg sodium hydrogen carbonate). , Potassium hydrogen carbonate), alkali metal silicates (eg sodium silicate, potassium silicate) alkali metal metasilicates (eg sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine , Tetraalkylammonium hydroxides (eg tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.01 to 30% by mass and the pH is 8 to 1
4 is preferable.

Suitable water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-
Propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-
Examples include butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. . The concentration of the water-miscible organic solvent is generally 0.1 to 30% by mass.

A known surfactant may be added to the developing solution. The developing solution can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photosensitive resin layer, a method such as rubbing with a rotating brush in a developing solution or rubbing with a wet sponge, or a method of utilizing the spray pressure when the developing solution is sprayed is appropriately used. be able to. The temperature of the developer is usually around room temperature to 40 ° C.
Is preferred. It is also possible to include a water washing step after the development processing. Further, the development may be carried out by treating the alkali-soluble thermoplastic resin layer, the oxygen barrier layer and the photosensitive resin layer at a time, but the uneven development and the deterioration of the layer due to the developing solution at the time of the development of the photosensitive resin layer are reduced. Therefore, it is preferable to develop the photosensitive resin layer after first dissolving and removing the alkali-soluble thermoplastic resin layer and the oxygen blocking layer. When the photosensitive resin layer is developed later, it is preferable that the developer used for removing the alkali-soluble thermoplastic resin layer and the oxygen blocking layer is selected so as not to deteriorate the photosensitive resin layer.
This method, by selecting a developer in consideration of the difference in dissolution rate between the alkali-soluble thermoplastic resin layer and the oxygen barrier layer, and the photosensitive resin layer, or by the liquid temperature, spray pressure,
It can be carried out by appropriately combining development processing conditions such as pressure when rubbing. By this method, uneven development can be suppressed.

After the developing step, heat treatment is performed. That is, the support having the photosensitive resin layer photocured by exposure is heated in an electric furnace or a dryer, or the photosensitive resin layer is irradiated with an infrared lamp to be heated. The heating temperature and time depend on the composition and thickness of the photosensitive resin layer, but generally, in order to obtain sufficient solvent resistance and alkali resistance,
It is preferable to heat at about 120 to 250 ° C. for about 10 to 300 minutes.

The image forming material of the present invention can be basically advantageously used for producing a multicolor image such as a color filter, but in addition, an interlayer insulating film, a printed wiring board,
It can be used for intaglio letterpress printing plates, name plates, color proofs, offset printing plates, screen printing stencils and the like. A known copper-clad laminate is generally used as a substrate for producing a printed wiring board.

[0056]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. Unless otherwise specified in the text, "part"
Means "parts by mass". Synthesis of Surfactants S1 to S5 of the Present Invention Using the monomers (a), (b) and (c) shown in Table 1, the surfactants of the present invention having the mass average molecular weight shown in the same table were synthesized. .

[0057]

[Table 1]

Preparation of Thermoplastic Resin Layer Forming Coating Liquid C11 A thermoplastic resin layer forming coating liquid having the following composition C11 was prepared.

[0059] Composition C11 of coating liquid for forming thermoplastic resin layer: ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzylmethac Relate / methacrylic acid copolymer 14.0 parts (Copolymerization composition ratio (molar ratio) = 55/30/10/5, mass average molecular weight = 100,000, (Tg: approx. 70 ° C) ・ Styrene / acrylic acid copolymer 6.0 parts (Copolymerization composition ratio (molar ratio) = 65/35, mass average molecular weight = 10,000, Tg: about 10 ℃) ・ 2 equivalents of octaethylene glycol monomethacrylate to bisphenol A 5.0 parts of dehydrated and condensed compound (BPE-500: manufactured by Shin Nakamura Chemical Co., Ltd.) ・ Methyl ethyl ketone 50.0 parts ・ Methanol 10.0 parts · 3.0 parts of surfactant S1 for the present invention  (Used as a 20% by mass solution of methyl isobutyl ketone, and the number of solutes)

Coating liquid C12 to 17 for forming thermoplastic resin layer
Preparation of thermoplastic resin layer-forming coating liquid C11 was prepared by changing the type and amount of the surfactant of the present invention as shown in Table 2.

Preparation of coating solution C18 for forming thermoplastic resin layer In the preparation of coating solution C11 for forming thermoplastic resin layer, a surfactant for use in the present invention was not used. Preparation of Thermoplastic Resin Layer Forming Coating Liquid C19 In preparation of the thermoplastic resin layer forming coating liquid C11, a fluorochemical surfactant A: C ₈ F instead of the surfactant of the present invention.
₁₇ SO ₂ N (C ₄ H ₉ ) CH ₂ CH ₂ OCOCH = CH ₂ 60
Wt% and _{H (O (CH 3) CHCH} 2) 6 OCOCH = C
A copolymer containing 40% by mass of H ₂ (mass average molecular weight: 30,000, 20% by mass solution of methyl isobutyl ketone) was similarly prepared. Preparation of coating liquid C20 for forming thermoplastic resin layer In the preparation of coating liquid C11 for forming thermoplastic resin layer, instead of the surfactant for the present invention, Megafac F142-
D (manufactured by Dainippon Ink and Chemicals, Inc.) was prepared in the same manner by using an equal mass part of the solid content.

Composition R1 of coating liquid for forming red photosensitive resin layer
Preparation of 1 A coating liquid for forming a red photosensitive resin layer having the following composition R11 was prepared. Composition of coating liquid for forming red photosensitive resin layer R11: benzyl methacrylate / methacrylic acid copolymer 60.0 parts (molar ratio = 73/27, acid value = 73 mgKOH / g, mass average molecular weight = 30,000, viscosity = 0.12 Pa · s) Pentaerythritol tetraacrylate 43.2 parts Michler's ketone 2.4 parts 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 2.5 parts Irgadine Red BPT 5. 4 parts-Methyl cellosolve acetate 560 parts-Methyl ethyl ketone 280 parts-Fluorosurfactant A 1.0 parts (Used as a 20% by mass solution of methyl isobutyl ketone, the number of solutes)

Coating liquids R12 to 1 for forming red photosensitive resin layer
Preparation of 7 In the preparation of the coating liquid R11 for forming the red photosensitive resin layer,
The surfactant for use in the present invention was prepared by changing the kind and the addition amount thereof as shown in Table 2.

Preparation of coating liquid R18 for forming red photosensitive resin layer In preparing coating liquid R11 for forming red photosensitive resin layer,
It was prepared without using the surfactant for the present invention. Preparation of coating liquid R19 for forming red photosensitive resin layer In preparing coating liquid R11 for forming red photosensitive resin layer,
C ₈ F ₁₇ SO ₂ N (C ₄ H ₉ ) instead of the surfactant for the present invention
CH ₂ CH ₂ OCOCH = CH ₂ 60% by mass and H (O (C
H ₃ ) CHCH ₂ ) ₆ OCOCH = CH ₂ 40 mass% of a copolymer (mass average molecular weight: 30,000, methyl isobutyl ketone 20 mass% solution) was similarly prepared. Preparation of coating liquid R20 for forming red photosensitive resin layer In preparation of coating liquid R11 for forming red photosensitive resin layer,
Instead of the surfactant for the present invention, Megafac F142
-D (manufactured by Dainippon Ink and Chemicals, Inc.) was similarly prepared by using an equal amount by mass of solid content.

The performances of the above-prepared coating solution for forming a thermoplastic resin layer and coating solution for forming a red photosensitive resin layer were evaluated by the following, and the results are shown in Tables 2 and 3. (1) Coating surface condition (coating unevenness) 20 ml of the coating solution is applied onto a support (PET) by spin coating.
/ M ^{2 and} apply a dry air of 5 m / min at 60 ° C. for 30 seconds to dry. Measure the areas with no unevenness, the areas with high density and the areas with low density with a densitometer and compare. ◎ Concentration change is within 1%. ○ The change in concentration is within 2%. △ Concentration change is within 5%. × The change in density is larger than 5%. (2) The thickness of the uneven surface support is measured when it is provided so that the dry film thickness becomes a predetermined value, and the change width between the maximum value, the minimum value, and the average value is examined. ◎ Within 3% ○ Within 5% △ Within 7% × No more than this (3) Repelling A certain area was applied and the presence or absence of repelling with a diameter of 2 mm or more was examined visually or with a magnifying glass. ◎ None at all ○ Slightly but not problematic for practical use △ Slightly occurs × Occurs and cannot be used (4) Pinholes Apply a certain area and count the holes that are 3 mm or more in diameter. ◎ None at all ○ Slightly but no problem in practical use △ Slightly occurred × Occurred and unusable

[0066]

[Table 2]

[0067]

[Table 3]

Examples 1 to 14 and Comparative Examples 1 to 3 On a support of a polyethylene terephthalate film having a thickness of 50 μm, the coating solution for forming a thermoplastic resin layer shown in Table 3 was spin-coated and dried to obtain a dry film thickness. 20 μm of an alkali-soluble thermoplastic resin layer was provided. Next, a coating solution having the following composition P1 was spin-coated on the thermoplastic resin layer and dried to provide an oxygen barrier layer having a dry film thickness of 1.6 μm. Composition of coating liquid for forming oxygen barrier layer P1: -Polyvinyl alcohol 100 parts (PVA205 manufactured by Kuraray Co., saponification degree: 88%)-Polyvinylpyrrolidone 50 parts (PVA manufactured by CAF Corporation, K-90) -Fluorine Surfactant 2 parts (Surflon S-131 manufactured by Asahi Glass Co., Ltd.)-Distilled water 3000 parts On the support having the thermoplastic resin layer and the oxygen barrier layer, the red photosensitive resin shown in Table 3 is used. The layer forming coating solution is spin-coated and dried to form a red photosensitive resin layer having a dry film thickness of 2 μm, and a polypropylene (12 μm thick) coating sheet is pressure-bonded onto the red photosensitive resin layer. do it,
An image forming material was prepared.

The coating sheet of the obtained image-forming material was peeled off, and the surface of the red photosensitive resin layer was laminated on a glass substrate (thickness: 1.1 mm) with a laminator (Taisei Laminator Co., Ltd.).
VP-II manufactured by Pressurization (10 kg / cm ² ) (≈
980 kPa), heated (100 ° C.) and bonded at a speed of 10 m / min, and then peeled at the interface between the support and the thermoplastic resin layer, and then a commercially available tape is adhered on the thermoplastic resin layer for 180 ° The peeled state of the tensile transfer layer was examined with to determine the adhesion to the glass substrate. The results are shown in Table 4. ◎ No peeling was observed. ○ Peeling was slightly, but there was no problem in practical use. △ Peeling occurred. × The film can be removed completely.

Preparation of color filter The covering sheet of the obtained image-forming material was peeled off, and the surface of the red photosensitive resin layer was covered with a glass substrate (thickness: 1.1 mm).
Laminator (VP-I manufactured by Taisei Laminator Co., Ltd.) on the surface
I) using pressure (10 kg / cm ² ) (≈980 kP
a), heating (130 ° C.) to bond them together, followed by peeling at the interface between the support and the thermoplastic resin layer to remove the support. Then, the red photosensitive resin layer was exposed through a photomask (a negative image of square pixels having a side of 20 to 60 μm) using an ultrahigh pressure mercury lamp. Exposure dose is 20 mJ / cm ²
Met. Then, the thermoplastic resin layer and the oxygen barrier layer were dissolved and removed in 30 seconds using a 1% triethanolamine aqueous solution. At this time, the photosensitive resin layer was not substantially developed. Then, the photosensitive resin layer was developed using a 1% sodium carbonate aqueous solution to remove the unexposed portion, thereby forming a pattern of red pixels (R). The glass substrate having red pixels was heated at 220 ° C. for 130 minutes to sufficiently cure the pixel portion to obtain a color filter having only red pixels. The surface of each of the obtained color filters was visually or microscopically observed and evaluated as follows. The results obtained are shown in Table 1. A: No color unevenness is observed. B: Color unevenness is slightly seen. C: Some color unevenness is seen. D: Many color irregularities are seen. E: Color unevenness is seen on the entire surface. The practical level is C or higher.

[0071]

[Table 4]

Example 15 On a support of a polyethylene terephthalate film having a thickness of 100 μm, a coating solution for forming a thermoplastic resin layer having the following composition C2 was spin-coated, dried and dried with an alkali to a dry film thickness of 20 μm. A different thermoplastic resin layer was provided.

[0073] Composition C2 of coating liquid for forming thermoplastic resin layer: ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzylmethac Relate / methacrylic acid copolymer 15 parts (Copolymerization composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5, mass average molecule Amount = 90,000) ・ Polypropylene glycol diacrylate 6.5 parts (Mass average molecular weight = 822) ・ Tetraethylene glycol dimethacrylate 1.5 parts ・ P-toluenesulfonamide 0.5 part ・ Benzophenone 1.0 part ・ Methyl ethyl ketone 30 parts

Next, the following composition P was formed on the thermoplastic resin layer.
The coating liquid of 2 was spin-coated and dried to provide an oxygen barrier layer having a dry film thickness of 1.6 μm. Composition of coating liquid for forming oxygen barrier layer P2: -Polyvinyl alcohol 100 parts (PVA 205 manufactured by Kuraray Co., saponification degree: 88%)-Polyvinylpyrrolidone 50 parts (PVA manufactured by CAF Corporation, K-90) -Fluorine Surfactant 2 parts (Surflon S-131 manufactured by Asahi Glass Co., Ltd.)-Distilled water 3000 parts

A coating solution for forming a red photosensitive resin layer comprising the following composition R20 and a composition G on each of the three supports having the thermoplastic resin layer and the oxygen barrier layer.
1. A green photosensitive resin layer forming coating liquid of 1, a blue photosensitive resin layer forming coating liquid of composition B1, and a black photosensitive resin layer forming coating liquid of composition K1 are spin-coated, dried, and dried. A red photosensitive resin layer having a film thickness of 2 μm was formed, and a polypropylene (12 μm thick) covering sheet was pressure-bonded onto the photosensitive resin layer to prepare an image forming material. Composition of coating liquid for forming red photosensitive resin layer R20: benzyl methacrylate / methacrylic acid copolymer 60.0 parts (molar ratio = 73/27, acid value = 73 mgKOH / g, mass average molecular weight = 30,000, viscosity = 0.12 Pa · s) Pentaerythritol tetraacrylate 43.2 parts Michler's ketone 2.4 parts 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 2.5 parts Irgadine Red BPT 5. 4 parts Methyl Cellosolve Acetate 560 parts Methyl Ethyl Ketone 280 parts Surfactant S2 0.3 parts of the present invention (Used as a 20 mass% solution of methyl isobutyl ketone and its solute parts) Green photosensitive resin layer forming coating liquid Composition G1: In the composition R20 of the coating liquid for forming the red photosensitive resin layer, 5.4 parts of Irgadine Red BPT Was replaced with 5.6 parts of copper phthalocyanine. Composition B1 of coating liquid for forming blue photosensitive resin layer: In composition R20 of coating liquid for forming red photosensitive resin layer, 5.4 parts of Irgadine Red BPT was replaced with 5.2 parts of Sudan Blue. Composition K1 of coating liquid for forming black photosensitive resin layer: In composition R20 of coating liquid for forming red photosensitive resin layer, 5.4 parts of Irgadine Red BPT was replaced with 10 parts of carbon black. The above-mentioned coating liquids for forming each photosensitive resin layer were prepared by the following method. First, dispersions of three kinds of pigments having respective hues were prepared by the following method. Each of the above pigments 360
g, dispersant (Solsperse 24000, manufactured by Zeneca) 3
6 g, and 740 g of a binder resin solution (40% by mass of a methyl cellosolve acetate solution of the above-mentioned benzyl methacrylate / methacrylic acid copolymer) kneader (Moriyama Seisakusho s
The pigment composition was obtained by kneading with 1-1) for 30 minutes. Next, 900 g of dispersion solvent (methyl cellosolve acetate)
After the addition, dispersion was further carried out for 360 minutes with a media mill (Dyno Mill KDL-PIL0T manufactured by Willie Ebbakochen). Pentaerythritol tetraacrylate, Michler's ketone, etc. were added to this dispersion to give the above composition.

The performance of each coating solution having the composition R21, G1, B1 or K1 was evaluated in the same manner as above, and the results are shown in Table 5. A color filter was produced by the following method using the image forming material. The coating sheet of the red image forming material was peeled off, and the surface of the red photosensitive resin layer was pressed (10 kg) on the glass substrate (thickness 1.1 mm) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.). / C
m ² ) (≈980 kPa), heating (130 ° C.) to bond them together, followed by peeling at the interface between the support and the thermoplastic resin layer to remove the support. Then, it was exposed to light through a predetermined photomask to remove the thermoplastic resin layer and the oxygen barrier layer using a 1% triethanolamine aqueous solution. At this time, the photosensitive resin layer was not substantially developed. Next, the photosensitive resin layer was developed using a 1% sodium carbonate aqueous solution to remove the unexposed portion (unnecessary portion), and a pattern of red pixels (R) was formed on the glass substrate. Then, on the glass substrate on which the pattern image forming material of red pixels is formed,
The green image-forming material is laminated in the same manner as above, peeled,
Exposure and development were performed to form a green pixel pattern. The same process was repeated for the blue image forming material and the black image forming material to form a color filter on the transparent glass substrate. In these steps, the adhesion between the glass substrate and the photosensitive resin layer was good. Comparative Example 4 In the compositions R21, G1, B1 and K1 of Example 12, the coating solution R2 in which the surfactant for the present invention was not added
2, G2, B2 and K2 were prepared, and a color filter was produced in the same manner as in Example 12. As a result, coating unevenness occurred. Further, the performances of the coating liquids R22, G2, B2 and K2 were evaluated in the same manner as above, and are shown in Table 5.

[0077]

[Table 5]

[0078]

As described above, according to the present invention, there is no coating unevenness, the coated surface is smooth, the layer thickness is uniform, and there is no color unevenness.
It is possible to provide a coating liquid having no pinhole and excellent in adhesiveness to a glass substrate, and an image forming material carrying the coating liquid.

[Brief description of drawings]

FIG. 1 is a cross-sectional view illustrating an example of a layer structure of an image forming material.

[Explanation of symbols]

1 support 2 Alkali-soluble thermoplastic resin layer 3 oxygen barrier 4 Photosensitive resin layer

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA18 AB13 CC04 CC11 EA05                       FA17                 2H048 BA45 BA47 BA48 BB14 BB28                       BB42                 4J100 AL08P AL08Q BA02P BA03Q                       BA04Q BA08Q BA28P BA51P                       BB17P CA04 JA37 JA38

Claims (2)

[Claims] 1. An image forming material comprising a support and a coating layer comprising at least an alkali-soluble thermoplastic resin layer and a photosensitive resin layer provided in this order on the support, wherein the thermoplastic resin layer and the photosensitive resin layer are provided. An image forming material containing a copolymer containing a monomer represented by the general formula (a) or (b) in at least one of the above. [Chemical 1] (In the formula, R ₀₁ , R ₀₂ and R ₀₃ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ₁ contains a single bond or at least one of an oxygen atom, a nitrogen atom and a sulfur atom. Represents a linking group, n is an integer of 1 to 20, and m is 2.
Is an integer of 1 to 14, l is an integer of 0 to 10, p is an integer of 2 to 10, and q is an integer of 1 to 30. ) 2. The image forming material according to claim 1, wherein at least the photosensitive resin layer of the coating layer is provided by spin coating.