TW201807488A - Photosensitive resin composition for light-sielding film, display substrate and manufacturing method thereof - Google Patents

Abstract

The present invention relates a photosensitive resin composition for light-shielding film, a display substrate and a manufacturing method of the display substrate. The photosensitive resin composition for light-shielding film is suitable for forming a light-shielding film on a substrate with a heat-resistant temperature of 160 DEG C or less, and the light-shielding film is excellent in solvent resistance and alkali resistance. The photosensitive resin composition for light-shielding film contains (A) polymerizable unsaturated group-containing alkali-soluble resin which has a structure of an epoxy (meth) acrylate acid addition product, (B) a photopolymerizable monomer with at least three ethylene unsaturated bonds, (C) an oxime ester-based polymerization initiator, (D) an azo-based polymerization initiator and (E) at least one selected from the group consisting of a black organic pigment, a mixed organic pigment and a light-shielding material.

Description

Photosensitive resin composition for light-shielding film, substrate for display and manufacturing method thereof

The present invention relates to a photosensitive resin composition for a light-shielding film, a display substrate provided with a light-shielding film obtained by curing the photosensitive resin composition for a light-shielding film, and a method for manufacturing a display substrate. Specifically, the present invention The present invention relates to a display for a light-shielding film photosensitive resin composition suitable for forming a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or lower, and a light-shielding film provided with a cured film on the substrate as the light-shielding film photosensitive resin composition. Substrate and method for manufacturing the display substrate.

Recently, for the purpose of flexible or one chip of a component, for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) is required. And other plastic substrates (plastic film, resin film) to directly form a light-shielding film (light-shielding pattern), or have organic electroluminescence (EL) or organic thin-film transistor (Thin Film Transistor, TFT) on a glass substrate or silicon wafer ) And other elements directly form a light-shielding film. However, in these cases, the heat-resistant temperature of the plastic substrate itself or the heat-resistant temperature of the component is low, and in most cases, the heat resistance is only about 160 ° C. at most. Therefore, when a light-shielding film is formed on a plastic substrate or a component, the film strength becomes insufficient at a thermal firing temperature below 160 ° C. In subsequent subsequent steps (such as each Red Green Blue (RGB) resist) Agent application, alkali resistance, etc.) have problems such as thinning of the coating film, rough surface, and pattern peeling.

Therefore, for example, Japanese Patent Laid-Open No. 2003-15288 (Patent Document 1) discloses a substrate obtained by coating, exposing, patterning, and thermally firing a plastic substrate on a plastic substrate using a photosensitive resin composition. The photosensitive resin composition uses an alkali-soluble resin of an acrylic copolymer as a matrix and contains a thermal polymerization initiator in addition to the photopolymerization initiator. Although the residue and the adhesion to the substrate are ensured (peel test), The pattern line width, development tolerance, reliability (solvent resistance, alkali resistance), etc. are not described, and these characteristics are not sufficient.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-15288

[Problems to be Solved by the Invention]

The present invention has been made in view of the problems described above, and an object thereof is to provide a photosensitive resin composition for a light-shielding film, which is suitable for forming on a plastic substrate or element having a heat resistance of at most 160 ° C. The light-shielding film can obtain a light-shielding film excellent in solvent resistance or alkali resistance even to these plastic substrates or devices having low heat resistance. The present invention also provides a display substrate including a light-shielding film obtained by curing the photosensitive resin composition for a light-shielding film, and a method for producing the same.

[Technical means to solve the problem]

Therefore, the present inventors have developed a photosensitive resin composition for a light-shielding film that obtains good development adhesion or linearity of a pattern by thermal curing at 160 ° C. or lower, and can obtain a light-shielding film excellent in solvent resistance or alkali resistance. After conducting diligent research, it was found that the combination of two types of specific polymerization initiators containing a predetermined alkali-soluble resin containing a polymerizable unsaturated group, a photopolymerizable monomer, a light-shielding component, and a solvent can solve the above problem. The problems as described above have completed the present invention.

That is, the gist of the present invention is as follows.

(1) A photosensitive resin composition for a light-shielding film, which contains the following components (A) to (E) as essential components, and (A) has a structure of an epoxy (meth) acrylate acid adduct Polymerizable unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) an oxime ester polymerization initiator, (D) an azo polymerization initiator And (E) one or more light-shielding components selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-shielding material.

(2) The photosensitive resin composition for a light-shielding film according to (1), wherein the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is represented by the following general formula (II),

[Chemical 1]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and A represents -CO -, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9, 9-diyl or directly bonded, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z- (COOH) _m (wherein Z represents a divalent carboxylic acid residue Or a trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20).

(3) The photosensitive resin composition for a light-shielding film according to (1) or (2), wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 50/50 to 90/10, with respect to 100 parts by mass of the total of the (A) component and the (B) component, the (C) component is 2 to 30 parts by mass and the (D) component is 1 to 20 parts by mass. The solid content containing the component which becomes the solid content by the photocuring of the photosensitive resin composition for light-shielding films contains (E) component of 40 mass%-70 mass%.

(4) The photosensitive resin composition for light-shielding films as described in any one of (1) to (3) whose (E) component is carbon black.

(5) A display substrate, which is a display substrate provided with a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or less, wherein the light-shielding film contains the following components (A) to (E) A photosensitive resin composition for a light-shielding film whose components are essential components is cured, (A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct, (B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds, (C) an oxime ester-based polymerization initiator, (D) an azo-based polymerization initiator, and (E) selected from a black organic pigment, a mixed-color organic pigment, and One or more light-shielding components in a group of light-shielding materials.

(6) A method for manufacturing a display substrate, which manufactures a display substrate having a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or less, and the method for manufacturing the display substrate is characterized by including the following (A) Component to (E) component A photosensitive resin composition for a light-shielding film as an essential component is applied to a substrate, exposed through a photomask, unexposed portions are removed by development, and then heated at 160 ° C or lower to form a predetermined pattern Light-shielding film, (A) an alkali-soluble resin containing a polymerizable unsaturated group having a structure of an epoxy (meth) acrylate acid adduct, and (B) photopolymerizable properties having at least three ethylenically unsaturated bonds A monomer, (C) an oxime ester polymerization initiator, (D) an azo polymerization initiator, and (E) one or more light-shielding members selected from the group consisting of a black organic pigment, a color-mixing organic pigment, and a light-shielding material ingredient.

[Effect of the invention]

The photosensitive resin composition for a light-shielding film of the present invention can form a line width of 5 μm even if the process of manufacturing a light-shielding film does not include a step of thermally curing at a temperature exceeding 160 ° C. A light-shielding film (light-shielding pattern) having excellent development adhesion, linearity, and good solvent resistance at 15 μm, especially 10 μm or less. Therefore, a light-shielding film can be formed on resin-made films such as PET and PEN having a heat resistance of 160 ° C or lower, or elements including organic EL or organic TFTs formed on a glass substrate or a silicon wafer. A light-shielding film for a display substrate.

That is, as in the present invention, a polymerizable unsaturated group-containing alkali-soluble resin having a specific structure, a polymerizable monomer having three or more ethylenically unsaturated groups, an oxime ester-based polymerization initiator, and an azo-based resin are used. The photosensitive resin composition having a polymerization initiator and a light-shielding component as essential components can form a desired light-shielding film on a substrate having low heat resistance with a heat resistance of 160 ° C. or lower, and can be used as a display substrate having various functions.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

Hereinafter, the present invention will be described in detail.

First, each component of the photosensitive resin composition for light-shielding films of this invention is demonstrated.

The polymerizable unsaturated group-containing alkali-soluble resin of the component (A) of the present invention has a structure of an epoxy (meth) acrylate acid adduct, and in particular, it is a resin having two or more epoxy groups. A compound obtained by reacting a compound with a (meth) acrylic acid (which means "acrylic and / or methacrylic acid") with a polycarboxylic acid or an anhydride thereof. To explain in detail using a preferred example, in order to react an epoxy compound represented by the following general formula (I) with (meth) acrylic acid, the obtained compound having a hydroxyl group and (a) a dicarboxylic acid or a tricarboxylic acid are reacted. Or (b) an epoxy (meth) acrylate acid adduct obtained by the reaction of (b) a tetracarboxylic acid or an acid dianhydride thereof. The epoxy compound represented by the general formula (I) refers to an epoxy compound obtained by reacting a bisphenol with an epihalohydrin or an equivalent thereof. (A) Since a component has a polymerizable unsaturated double bond and a carboxyl group, it imparts excellent photocurability, good developability, and patterning characteristics to a photosensitive resin composition, and improves the physical properties of a light-shielding film.

[Chemical 2] However, in the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and A represents -CO-, -SO ₂ -, -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, fluorene-9,9-diyl or directly bonded , L represents the average value of 0-10.

Examples of the bisphenols forming the epoxy compound of the general formula (I) include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, and bis (4- Hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) fluorene, bis (4-hydroxy-3,5-dimethylphenyl) fluorene, bis (4-hydroxy-3,5 -Dichlorophenyl) fluorene, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5- Dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3 , 5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5- Dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4 -Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane , Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9- Bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9 -Bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene , 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4 -Hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-bisphenol, 3,3'-bisphenol Wait. Among them, bisphenols forming an epoxy compound in which A in the general formula (I) is a fluorene-9,9-diyl group can be particularly preferably used.

The compound of general formula (I) for deriving the alkali-soluble resin (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the bisphenols with epichlorohydrin. In this reaction, l is usually mixed with a plurality of values due to oligomerization of a diglycidyl ether compound, and therefore has an average value of 0 to 10 (not limited to an integer), and a preferred average value of l is 0 to 3. When the average value of l exceeds the upper limit value, when the photosensitive resin composition is made of the alkali-soluble resin synthesized using the epoxy compound, the viscosity of the composition becomes too large to smoothly apply, or it is not sufficient. Alkali solubility is imparted and alkali developability becomes very poor.

As the (a) dicarboxylic acid or tricarboxylic acid or anhydride used for the epoxy (meth) acrylate acid adduct, a chain hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride or alicyclic dicarboxylic acid can be used. Or tricarboxylic acid or anhydride thereof, aromatic dicarboxylic acid or tricarboxylic acid or anhydride thereof. Here, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an anhydride thereof includes, for example, succinic acid, acetosuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, Compounds such as malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, or their anhydrides can also be further introduced A dicarboxylic acid or tricarboxylic acid or an anhydride thereof having an arbitrary substituent. Examples of the alicyclic dicarboxylic acid or tricarboxylic acid or its anhydride include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornanedicarboxylic acid. A compound such as an acid or an anhydride thereof may be a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof to which an optional substituent is further introduced. Furthermore, the aromatic dicarboxylic acid or tricarboxylic acid or its anhydride includes a compound such as phthalic acid, isophthalic acid, trimellitic acid, or the anhydride thereof, and it may be a dicarboxylic acid further introduced with an optional substituent. Or tricarboxylic acid or its anhydride.

The (b) tetracarboxylic acid or acid dianhydride used in the epoxy (meth) acrylate acid adduct may be a chain hydrocarbon tetracarboxylic acid or acid dianhydride or an alicyclic tetracarboxylic acid or An acid dianhydride, or an aromatic polycarboxylic acid or an acid dianhydride thereof. Here, the chain hydrocarbon tetracarboxylic acid or an acid dianhydride thereof may include a compound such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid or an acid dianhydride thereof, and an optional substituent may be further introduced. Tetracarboxylic acid or its acid dianhydride. Examples of the alicyclic tetracarboxylic acid or its dianhydride include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cyclopentane tetracarboxylic acid, norbornane tetracarboxylic acid, and the like. The compound or its acid dianhydride may be a tetracarboxylic acid or its acid dianhydride to which an arbitrary substituent is further introduced. Furthermore, examples of the aromatic tetracarboxylic acid or an acid dianhydride thereof include compounds such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, and diphenyl ether tetracarboxylic acid, or an acid dianhydride thereof. It may be a tetracarboxylic acid or an acid dianhydride in which an arbitrary substituent is further introduced.

Molar ratio of (a) dicarboxylic acid or tricarboxylic acid or its anhydride to (b) tetracarboxylic acid or its acid dianhydride used in epoxy (meth) acrylate acid adducts (a) / (b) It is preferably 0.01 to 10.0, and more preferably 0.02 or more and less than 3.0. If the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight of the photosensitive resin composition having high light-shielding, high resistance, and good photo-patternability cannot be obtained according to the present invention. . In addition, the smaller the molar ratio (a) / (b), the larger the molecular weight becomes, and the alkali solubility tends to deteriorate.

The epoxy (meth) acrylic acid adduct can be produced by the above-mentioned steps by a known method, for example, a method described in Japanese Patent Laid-Open No. 8-278629 or Japanese Patent Laid-Open No. 2008-9401. . First, a method of reacting (meth) acrylic acid with an epoxy compound of the general formula (I) includes, for example, the following method: (meth) acrylic acid having an epoxy group of the epoxy compound in an equimolar amount is added to a solvent, and In the presence of a catalyst (triethylbenzyl ammonium chloride, 2,6-diisobutylphenol, etc.), it is heated and stirred at 90 ° C to 120 ° C while blowing air to cause a reaction. Then, the method of reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product is as follows: an epoxy acrylate compound and a predetermined amount of an acid dianhydride and an acid monoanhydride are added to a solvent, and a catalyst (brominated In the presence of tetraethylammonium, triphenylphosphine, etc.), the reaction is carried out by heating and stirring at 90 ° C to 130 ° C.

The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 2,000 to 10,000, and more preferably in the range of 3,000 to 7,000. When the weight average molecular weight (Mw) is less than 2000, pattern adhesion during development using the photosensitive resin composition (A) cannot be maintained, and pattern peeling occurs, and if the weight average molecular weight (Mw) exceeds 10,000, development residues Or the residual film of the unexposed part is likely to remain. Further, (A) is preferably in a range of an acid value of 80 mgKOH / g to 120 mgKOH / g. If the value is less than 80 mgKOH / g, the residue during the alkali development of the photosensitive resin composition using (A) tends to remain, and if it exceeds 120 mgKOH / g, the alkali developing solution is applied to the photosensitive resin composition using (A). Penetration in the substrate became too fast, and peeling and development occurred, so that both were defective. The polymerizable unsaturated group-containing alkali-soluble resin (A) may be used alone, or a mixture of two or more thereof may be used.

(B) Examples of the photopolymerizable monomer having at least three ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate and trimethylolethane tri (meth) acrylic acid. Ester, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, alkylene oxide modified hexa (meth) acrylate of phosphazene, caprolactone (Meth) acrylates such as ester-modified dipentaerythritol hexa (meth) acrylate, dendrimer type multifunctional acrylates, hyperbranch type multifunctional acrylates, etc., can be used One or two or more of these compounds. Further, (B) the photopolymerizable monomer having at least three ethylenically unsaturated bonds does not have a free carboxyl group. In the present invention, a trifunctional or higher photopolymerizable monomer is used in order to obtain a sufficient crosslink density only by a heat treatment at 160 ° C or lower.

The blending ratio of these components (A) and (B) is preferably 50/50 to 90/10 in terms of mass ratio (A) / (B), and more preferably 60/40 to 80/20. If the blending ratio of the component (A) is less than 50/50 in terms of (A) / (B), the following problems occur: the cured product after photo-hardening becomes brittle, and the acid value of the coating film in the unexposed portion is low, so The solubility in the alkali developer is reduced, the edges of the pattern become rough and uneven, etc. In addition, if (A) / (B) is more than 90/10, the following problems may occur: photoreactive functional groups in the resin The proportion is small and the crosslinked structure is not sufficiently formed. Furthermore, the acid value of the coating film of the exposed portion due to the resin component is too high, and the solubility of the exposed portion to the alkali developing solution is improved. Therefore, the pattern formed is more targeted than the target. The line width is thinner, or the pattern is easily missed.

Examples of the oxime ester-based polymerization initiator of the component (C) include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzylidene) Oxime), 1- (4- (phenylsulfonyl) phenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4- (methylsulfonyl) ) Phenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4- (methylsulfonyl) phenyl) butane-1-oneoxime-O-ethyl Acid ester, 1- [9-ethyl-6- (2-methylbenzylidene) oxazol-3-yl] ethanone = O-acetamidooxime, (9-ethyl-6-nitro Oxazol-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone = O-acetamidooxime, (8-{[(ethyl (Methoxy) imino] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl} -11- (2-ethylhexyl) -11H-benzo [a] pyrene Azol-5-yl) (2,4,6-trimethylphenyl) methanone, (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2- )-, Ethylamoxime, ethyl ketone, 1- [7- (2-methylbenzylidene) -9,9-dipropyl-9H-fluoren-2-yl]-, 1- (O -Ethynyloxime), ethyl ketone, 1-(-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1-O-ethynyloxime and the like. In addition, two or more of these oxime ester-based polymerization initiators may be used.

The main function of the oxime ester polymerization initiator of the component (C) is to initiate photoradical polymerization. The amount of the initiator used is based on the total of 100 parts by mass of the components (A) and (B), based on 2 to 30 parts by mass. The mass part is preferable, and 5 to 25 mass parts is preferable. When the blending ratio of the (C) component is less than 2 parts by mass, the speed of photopolymerization is slowed down and the sensitivity is reduced. On the other hand, when it exceeds 30 parts by mass, the following problems may occur: the sensitivity is too strong and becomes a pattern In a state where the line width is thicker than the pattern mask, the faithful line width cannot be reproduced to the mask, or the pattern edges become rough and uneven.

Examples of the azo-based polymerization initiator of the component (D) include azobisisobutyronitrile (10-hour half-life temperature (toluene) (hereinafter referred to as T _1/2 ) at 65 ° C), 2,2'-azo Bis (2,4-dimethylvaleronitrile) (51 ° C at T _1/2 ), dimethyl 2,2'-azobis (2-methylpropionate) (66 ° C at T _1/2 ) ), Dimethyl 1,1'-azobis (1-cyclohexanecarboxylic acid ester) (T _1/2 is 73 ° C), 1,1'-azobis (cyclohexane-1-carbonitrile) ) (T _1/2 is 88 ° C), 1,1'-azobis (1-ethoxyl-1-phenylethane) (T _1/2 is 61 ° C), dimethyl 2,2 '-Azobisisobutyrate (T _1/2 is 67 ° C), etc.

The function of the azo-based polymerization initiator of the component (D) is mainly to improve the thermal radical polymerizability of the photosensitive resin composition, and particularly to increase the thermal polymerization during post-baking after exposure and development. Physical properties of hardened materials such as pattern hardness. Therefore, it is necessary to add an appropriate amount of an azo-based polymerization initiator at an appropriate 10-hour half-life temperature (T _1/2 ) according to the post-baking conditions and the like. The preferred 10-hour half-life temperature is 50 ° C to 80 ° C. The amount of use thereof is preferably 1 to 20 parts by mass based on 100 parts by mass of the total of (A) component and (B) component. Part by mass to 15 parts by mass is suitable.

The component (E) is a light-shielding component selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-shielding material, and is preferably excellent in heat resistance, light resistance, and solvent resistance. Here, examples of the black organic pigment include perylene black, aniline black, cyanine black, and lactam black. Examples of the mixed-color organic pigment include a pigment that simulates blackening two or more pigments selected from red, blue, green, purple, yellow, cyan, and crimson. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, and titanium black. Two or more light-shielding components can be appropriately selected and used. In particular, carbon black is preferable in terms of light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. In addition, if the carbon black to be used is a carbon black whose surface is coated with a dye, a resin, or the like, it is suitable for the case where a hardened product having a high resistance is used.

Examples of the solvent of the component (F) include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, and terpenes such as α-terpineol and β-terpineol. , Ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve Agent, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Glycol ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate Acetates such as carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., by using these solvents By dissolving and mixing, a uniform solution-like composition can be prepared.

The light-shielding component of (E) is preferably prepared by dispersing the light-shielding component in the solvent (F) together with the (G) dispersant in advance, and then preparing a photosensitive resin composition for a light-shielding film. Here, the solvent to be dispersed can be used as long as it is the solvent mentioned in said (F) component, For example, a propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are used suitably. The blending ratio of the light-shielding component (E) forming the light-shielding dispersion is preferably used in a range of 40% to 70% by mass based on the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. The range of 40 to 60 mass% is particularly preferable. If it is less than 40% by mass, the light-shielding property is insufficient for high light-shielding purposes. If it exceeds 70% by mass, the following disadvantageous problems occur: the content of the photosensitive resin, which is originally a binder, is reduced, so that the developing characteristics are impaired, and the film-forming ability is impaired. In addition, the total solid content of the photosensitive resin composition for light-shielding films includes a component that becomes a solid content by photocuring the photosensitive resin composition for light-shielding films.

As the dispersant (G) to be used, well-known dispersants such as various polymer dispersants can be used. As a specific example of the dispersant, a well-known compound (a compound commercially available under the names of a dispersant, a dispersing wetting agent, and a dispersing accelerator, etc.) that has been used for pigment dispersion can be used without particular limitation, and examples thereof include cationic polymers Dispersant, anionic polymer dispersant, nonionic polymer dispersant, pigment derivative dispersant (dispersion aid), etc. Particularly suitable are cationic functional groups having imidazolyl, pyrrolyl, pyridyl, primary amino, secondary amino, or tertiary amino groups as the adsorption point for pigments, and the amine value is 1 mgKOH / g ～ 100 mgKOH / g A cationic polymer-based dispersant having a number average molecular weight in the range of 1,000 to 100,000. The blending amount of the dispersant is preferably 1% to 30% by mass, and more preferably 2% to 25% by mass based on the light-shielding component.

Furthermore, when preparing a light-shielding dispersion liquid, a part of the polymerizable unsaturated group-containing alkali-soluble resin (A) component is co-dispersed in addition to the dispersant, and when the photosensitive resin composition for a light-shielding film is prepared. It is easy to maintain the exposure sensitivity at a high sensitivity, and it can be made into a photosensitive resin composition which has good adhesion during development and does not easily cause the problem of residues. The blending amount of the (A) component at this time is preferably 2% by mass to 20% by mass in the light-shielding dispersion liquid, and more preferably 5% by mass to 15% by mass. When the (A) component is less than 2% by mass, effects such as sensitivity improvement, adhesion improvement, and residue reduction as co-dispersion effects cannot be obtained. In addition, if it exceeds 20% by mass, especially when the content of the light-shielding material is large, the viscosity of the light-shielding dispersion liquid is high, it is difficult to uniformly disperse, or it takes much time, and it is difficult to obtain a photosensitive resin combination for obtaining a high-resistance coating film. Thing. In addition, the obtained light-shielding dispersion liquid is mixed with (A) component, (B) component, (C) component, and (D) component, and if necessary, component (F) is added and adjusted to a viscosity suitable for film forming conditions. A photosensitive resin composition for a light-shielding film was prepared.

In addition, in the photosensitive resin composition of the present invention, if necessary, polymerization initiators other than oxime ester-based and azo-based polymerization initiators, chain transfer agents, sensitizers, non-photosensitive resins, hardening accelerators, antioxidants, and plastics may be blended. Additives such as chemical stabilizers, fillers, homogenizers, defoamers, coupling agents, surfactants, pigments and dyes for color adjustment. Examples of oxime ester-based and azo-based polymerization initiators include acetophenones, benzophenones, α-hydroxyalkyl phenones, α-aminoalkyl phenones, benzoin ethers, and Imidazole compounds, halogenated methyldiazole compounds, halogenated methyltriazine compounds, and the like. As the chain transfer agent and the sensitizer, a sulfur atom-containing compound can be generally used. Examples include thiol compounds, Disulfide compounds and the like are preferably exemplified by aliphatic polyfunctional thiols such as 1,4-bis (3-mercaptobutyryloxy) butane. Examples of the non-photosensitive resin include bisphenol epoxy resins, novolac epoxy resins, alicyclic epoxy resins, epoxy silicone resins, and the like. Examples of the antioxidant include hindered phenol antioxidants. And phosphorus-based antioxidants. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silicon dioxide, mica, and oxidation. Examples of the defoaming agent or leveling agent include aluminum, silicone, fluorine, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant. Examples of the coupling agent include 3- (glycidyloxy) propyltrimethoxysilane and 3-isocyanatepropyltriethyl. Silane coupling agents such as oxysilane and 3-ureidopropyltriethoxysilane.

The photosensitive resin composition of this invention suitably contains the said (A) component-(F) component as a main component. It is desirable that solid components other than the solvent (solid components include monomers which become solid components after curing) include (A) component to (E) component in a total amount of 80% by mass, preferably 90% by mass or more. . (F) The amount of the solvent varies depending on the target viscosity, and it is preferable to contain the solvent in the photosensitive resin composition in a range of 70% by mass to 90% by mass.

A method of forming a light-shielding film using the photosensitive resin composition for a light-shielding film of the present invention includes the following photolithography method. The following methods can be mentioned: firstly coating a photosensitive resin composition on a plastic substrate or a device, and then drying (pre-baking) the solvent, and then irradiating the film obtained in this manner with ultraviolet rays through a photomask to harden the exposed portion, Further, development and elution of an unexposed part using an alkaline aqueous solution are performed to form a pattern, and post-baking (hot calcination) is performed as post-curing.

Examples of the substrate to which the photosensitive resin composition of the present invention is applied include resin films (plastic substrates) such as PET and PEN having a heat resistance of 160 ° C. or lower. Here, the heat-resistant temperature is a temperature that does not cause problems such as deformation even if the substrate is exposed to a pattern such as a pattern that forms a light-shielding film on the substrate. It also varies depending on the degree of extension treatment of the resin film, but it must not exceed at least Glass transition temperature (Tg). Alternatively, a substrate on which an electrode such as indium tin oxide (ITO) or gold is vapor-deposited or patterned on a resin film may be exemplified as the substrate.

In addition, other examples of the substrate to which the photosensitive resin composition of the present invention is applied include a substrate in which a film having a low heat resistance is formed on a substrate having a high heat resistance such as a glass substrate or a silicon wafer. Specific examples include an element in which an organic EL (Organic Light Emitting Diode (OLED)) or an organic thin film transistor (TFT) is formed on a glass or a silicon wafer. In addition, although the heat resistance temperature of a substrate having low heat resistance, such as a resin film and a device, varies depending on the type of the resin and the device, it can be said to be generally 100 ° C to 160 ° C.

A method of applying a solution of the photosensitive resin composition on these substrates may be a method using a roll coater, a land coater, a slit coater, or a spinner in addition to the well-known solution dipping method and spray method. And other arbitrary methods. After coating to a desired thickness by these methods, the solvent is removed (pre-baking) to form a film. The pre-baking is performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time of the pre-baking are appropriately selected according to the solvent used, and for example, it is performed at a temperature of 60 ° C to 110 ° C for 1 minute to 3 minutes.

The exposure performed after the pre-baking is performed by an ultraviolet exposure device, and exposure is performed through a photomask, so that only the resist corresponding to the pattern is exposed to light. The exposure device and its exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a far-ultraviolet lamp, and the photosensitive resin composition in the coating film is light-cured.

The alkali development after exposure is performed in order to remove the resist of the unexposed part, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. In particular, sodium carbonate and potassium carbonate containing 0.05% to 3% by mass are used. It is preferable to develop a weakly alkaline aqueous solution of a carbonate such as lithium carbonate or the like at a temperature of 23 ° C. to 28 ° C., and a fine image can be precisely formed using a commercially available developing machine or ultrasonic cleaner.

After development, heat treatment (post-baking) is preferably performed at a temperature of 100 ° C to 160 ° C and under conditions of 20 minutes to 60 minutes. This post-baking is performed to improve the adhesion between the patterned light-shielding film and the substrate. This is performed in the same manner as the pre-baking by heating with an oven, a hot plate, or the like. The patterned light-shielding film of the present invention is formed through each step of the above-mentioned photolithography method.

As described above, the photosensitive resin composition of the present invention can be suitably used to form a light-shielding film on a substrate having a low heat-resistant temperature through operations such as exposure and alkali development, and is particularly suitable for the need for a fine light-shielding film. Pattern case. Specifically, when a substrate having a low heat-resistant temperature is used, it can be used to form a black matrix for a color filter or an organic EL element or a barrier material (for In the case of inkjet method to form RGB, etc.), light-shielding film, light-shielding film for touch screen, etc., these substrates with light-shielding film can also be used as components for display devices or imaging elements such as liquid crystal or organic EL (ie These are collectively referred to as a display substrate).

[Example]

Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these examples.

First, a synthesis example of the (A) polymerizable unsaturated group-containing alkali-soluble resin of the present invention is shown. The evaluation of the resin of the synthesis example was performed as follows.

[Solid content concentration]

1 g of the resin solution obtained in the synthesis example was impregnated in a glass screening program [weight: W ₀ (g)] and weighed [W ₁ (g)], and the weight was measured after heating at 160 ° C for 2 hours [ W ₂ (g)] The solid content concentration was determined from the following formula.

Solid content concentration (% by weight) = 100 × (W ₂ －W ₀ ) / (W ₁ －W ₀ )

[Acid value]

The resin solution was dissolved in dioxane, and the acid value was determined by titration with a 1/10 N-KOH aqueous solution using a potentiometric titration device [trade name COM-1600 manufactured by Hiranuma Sangyo Co., Ltd.].

[Molecular weight]

Gel Permeation Chromatography (GPC) [trade name HLC-8220GPC manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, column: TSK gel Super H-2000 (2) + TSK gel Super H-3000 (1) + TSK gel Super H-4000 (1) + TSK gel Super-H 5000 (1) [manufactured by Tosoh], temperature: 40 ° C, speed: 0.6 ml / min ] The measurement was performed, and the weight average molecular weight (Mw) was calculated as a standard polystyrene [PS-oligomer kit manufactured by Tosoh Co., Ltd.].

The abbreviations used in the synthesis examples are as follows.

BPFE: reactant of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxane. Among the compounds of the general formula (I), compounds in which A is fluorene-9,9-diyl, and R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen.

AA: Acrylic

BPDA: 3,3,4,4-biphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

MAA: methacrylic acid

MMA: methyl methacrylate

CHMA: cyclohexyl methacrylate

GMA: glycidyl methacrylate

TEAB: Tetraethylammonium bromide

AIBN: Azobisisobutyronitrile

TPP: Triphenylphosphine

DTBC: 2,6-di-tert-butyl-p-cresol

PGMEA: propylene glycol monomethyl ether acetate

DMDG: Diethylene glycol dimethyl ether

[Synthesis example 1]

A 500 ml four-necked flask with a reflux condenser was charged with 114.4 g (0.23 mol) of BPFE, 33.2 g (0.46 mol) of AA, 157 g of PGMEA, and 0.48 g of TEAB, and heated at 100 ° C to 105 ° C. Stir for 20 hours and react. Then, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were added to the flask, and stirred under heating at 120 ° C to 125 ° C for 6 hours to obtain an alkali-soluble resin (A) -1. The solid content concentration of the obtained resin solution was 56.1 wt%, the acid value (in terms of solid content) was 103 mgKOH / g, and the Mw obtained by GPC analysis was 3600.

[Synthesis example 2]

In a 1000 ml four-neck flask with a nitrogen introduction tube and a reflux tube, add 51.7 g (0.60 mol) of MAA, 38.0 g (0.38 mol) of MMA, 37.0 g (0.22 mol) of CHMA, 5.91 g of AIBN, and 295 g of DMDG was polymerized by stirring at 80 ° C to 85 ° C for 8 hours under a nitrogen stream. Furthermore, 39.8 g (0.28 mol) of GMA, 1.44 g of TPP, and 0.055 g of DTBC were added to the flask, and the mixture was stirred at 80 ° C to 85 ° C for 16 hours to obtain a polymerizable unsaturated group-containing (meth) acrylate. Resin (A) -2. The solid content concentration of the obtained resin solution was 35.5% by mass, the acid value (in terms of solid content) was 110 mgKOH / g, and the Mw obtained by GPC analysis was 18080.

Next, the present invention will be specifically described based on examples and comparative examples related to the production of a photosensitive resin composition for a light-shielding film and a cured product thereof, but the present invention is not limited to these examples. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions for light-shielding films and the cured products thereof in the following examples and comparative examples are as follows.

(Alkali-soluble resin containing polymerizable unsaturated group) (A) -1: Alkali-soluble resin solution obtained in Synthesis Example 1 (A) -2: Alkali-soluble resin solution obtained in Synthesis Example 2

(Photopolymerizable monomer) (B) -1: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Toa Kasei Corporation, trade name Aronix M-405) (B) -2: Trimethylolpropane triacrylate (manufactured by Sartomer Japan Co., Ltd., trade name SR351S) (B) -3: Ethylene Oxide (EO) adduct 2 of bisphenol A Acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name Light Acrylate BP-4EAL)

(Oxime ester polymerization initiator)

(C): Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-oxazol-3-yl]-, 1- (O-acetamidooxime) ( Manufactured by BASF Japan (Irgacure OXE02)

(Other than azo-based polymerization initiator) (D) -1: 2,2-Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-60) (D) -2: dimethyl 2, 2-Azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-601) (D) -3: 1,1'-azobis (1-acetamido- 1-phenylethane) (manufactured by Otsuka Chemical Co., Ltd., trade name: OTAZO-15) (D) -4: benzamidine peroxide (manufactured by Nippon Oil Company, trade name: Nyper) BMT-K40)

(Light-shielding disperse pigment)

(E): PGMEA dispersion with a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 4.75% by mass (solid content is 29.75%)

(Solvent) (F) -1: PGMEA (F) -2: Cyclohexanone

(Silane coupling agent)

(H): S-510 (manufactured by JNC)

(Surfactant) (I): Megaface F475 (manufactured by DIC)

The formulation components were blended at the ratios shown in Table 1 to prepare the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4. In addition, all the numerical values in Table 1 represent mass parts. In addition, (F) -1 and (F) -2 are the amounts which do not contain the solvent in (A) -1 and (A) -2 and the solvent in (E).

[Table 1]

[Evaluation]

The photosensitive resin compositions for black resists of Examples 1 to 6 and Comparative Examples 1 to 4 were used to perform the evaluations described below. The evaluation results of these evaluations are shown in Tables 2 and 3.

<Evaluation of development characteristics (pattern line width, pattern linearity)>

Using a spin coater, each of the obtained photosensitive resin compositions was coated on a 125 mm × 125 mm glass substrate (Corning 1737) so that the film thickness after baking was 1.2 μm, at 90 ° C. Pre-bake for 1 minute. Then, adjust the exposure gap to 100 μm, cover the dry coating film with a negative mask with line / gap = 10 μm / 50 μm, and irradiate 50 mJ / with an ultra-high pressure mercury lamp with i-ray illumination of 30 mW / cm ² cm ² of ultraviolet rays, which undergoes a photo-hardening reaction of the photosensitive portion.

Then, using a 25 ° C, 0.04% potassium hydroxide aqueous solution, the exposed coated plate was sprayed with a pressure of 1 kgf / cm ² from the development time (break time = BT) at which the pattern began to appear for +10 seconds. After +20 seconds of development, spray water washing at a pressure of 5 kgf / cm ^{2 was} performed to remove the unexposed portion of the coating film to form a light-shielding film pattern on the glass substrate. Then, a hot air dryer was used at 120 ° C for 60 minutes. Bake after heat. The obtained light-shielding film pattern was evaluated for line width and pattern linearity with respect to a mask width of a 10 μm line.

Pattern line width: The pattern line width of the mask width of 10 μm was measured using a length-measuring microscope (“XD-20” manufactured by Nikon Corporation).

Pattern linearity: Observe the 10 μm mask pattern after post-baking with an optical microscope, evaluate the case where no peeling of the substrate or the roughness of the pattern edge portion is confirmed as ○, and the partially confirmed case as △. The overall confirmed situation was evaluated as ×.

The evaluation of the pattern line width and the pattern linearity was performed in the case of BT + 10 seconds and the case of BT + 20 seconds.

<Evaluation of OD / μm>

Each of the obtained photosensitive resin compositions was coated on a 125 mm × 125 mm glass substrate (Corning 1737) so that the film thickness of the obtained photosensitive resin composition after baking was 1.1 μm using a spin coater at 90 ° C. Pre-bake for 1 minute. Then, without covering the negative mask, an ultra-high pressure mercury lamp with an i-ray illuminance of 30 mW / cm ² was irradiated with 80 mJ / cm ² of ultraviolet light to perform a photo-hardening reaction.

Then, the exposed coated plate was developed using a spray pressure of 1 kgf / cm ² at 25 ° C. and a 0.05% potassium hydroxide aqueous solution for 60 seconds, and then spray-washed with a pressure of 5 kgf / cm ² , and then dried using hot air. The machine was post-heated at 120 ° C for 60 minutes. A Macbeth transmission densitometer was used to evaluate the OD value of the coated plate. The film thickness of the light-shielding film formed on the coated plate was measured, and the value obtained by dividing the OD value by the film thickness was OD / μm.

＜ Evaluation of solvent resistance ＞

The coated plate (glass plate with a light-shielding film) produced in the same manner as in the OD evaluation was used to evaluate the solvent resistance of the formed coating film (light-shielding film). Using a rag dipped in PGMEA or cycloone (anone) to continuously rub, observe the surface state, and record the number of rubs when the surface of the coating film is dissolved or softened and damaged. A case where the number of times when any solvent was used was 20 or more was regarded as solvent resistance ○, and a case where it was less than 20 times was regarded as solvent resistance ×.

＜ Stability over time ＞

Relative to the initial solution viscosity of the prepared photosensitive resin solution, a case where the solution viscosity increased by 1.5 times or more the initial solution viscosity after being left at room temperature at 23 ° C for 5 days was regarded as ×, and a case less than 1.5 times was regarded as 〇.

[Table 2] ※ For the evaluation of the pattern line width and the linearity of the pattern, the left column is evaluated at BT + 10 seconds, and the right column is evaluated at BT + 20 seconds.

[table 3] ※ For the evaluation of the pattern line width and the linearity of the pattern, the left column is evaluated at BT + 10 seconds, and the right column is evaluated at BT + 20 seconds.

When the photosensitive resin composition solution for a light-shielding film of the present invention is used, as shown in Examples 1 to 6, the linearity of the pattern is maintained even after post-baking at a low temperature of 120 ° C., and PGMEA can be formed. Or cyclohexanone has a light-shielding film pattern that has sufficient solvent resistance, and also has sufficient storage stability as a photosensitive resin composition solution.

On the other hand, as in Comparative Example 1, if a difunctional monomer is used as the photopolymerizable monomer, the crosslinking density of the cured film after the post-baking cannot be sufficiently obtained, and the pattern is straight when the development time is slightly extended. Inferior performance and insufficient solvent resistance. As in Comparative Example 2, if a peroxide-based polymerization initiator is used instead of an azo-based polymerization initiator to impart thermal radical polymerizability, the storage stability as a photosensitive resin composition solution is insufficient. As in Comparative Example 3, without adding an azo-based polymerization initiator, when the post-baking temperature is low, sufficient solvent resistance cannot be obtained. As in Comparative Example 4, if an acrylic copolymer-based compound is used instead of the compound of the general formula (II) as the polymerizable unsaturated group-containing alkali-soluble resin, the crosslinking is not sufficiently performed at a low post-baking temperature. , A pattern with sufficiently good linearity cannot be obtained, and the solvent resistance is also insufficient.

[Industrial availability]

The photosensitive resin composition for a light-shielding film of the present invention can form a line width of 5 μm to 15 μm, especially 10 μm, even if the step of thermally curing at a temperature exceeding 160 ° C. is not included in the manufacturing process of the light-shielding film. A light-shielding film (light-shielding pattern) having excellent development adhesion or linearity and good solvent resistance in the following cases. Therefore, a light-shielding film having such characteristics can be formed on a resin film made of PET, PEN, or the like having a heat-resistant temperature of 160 ° C. or less, or an element including an organic EL or organic TFT on a glass substrate or a silicon wafer.

That is, the photosensitive resin composition for a light-shielding film of the present invention is suitable for, for example, installing a black matrix, a partition material, and a spacer having a light-shielding function, which are necessary for forming a color filter or an organic EL element on a substrate having a low heat-resistant temperature. A light-shielding film such as a column spacer, or a light-shielding film provided on a bezel portion necessary for forming a touch screen. These substrates with a light-shielding film (that is, a substrate for a display) can be used to manufacture liquid crystals. Display devices such as organic EL or solid-state imaging devices such as Complementary Metal Oxide Semiconductor (CMOS).

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be determined by the scope of the attached patent application.

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Claims (6)

A photosensitive resin composition for a light-shielding film, comprising the following components (A) to (E) as essential components, and (A) a polymerization-containing structure having an epoxy (meth) acrylate acid adduct (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds; (C) an oxime ester-based polymerization initiator; (D) an azo-based polymerization initiator; and ( E) One or more light-shielding components selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-shielding material. The photosensitive resin composition for a light-shielding film according to item 1 of the scope of patent application, wherein the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is represented by the following general formula (II), In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ represents a hydrogen atom or a methyl group, and A represents -CO- , -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 茀 -9,9-diyl Or directly bonded, X represents a tetravalent carboxylic acid residue, and Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z- (COOH) _m , where -OC-Z- (COOH) _m represents Z For a divalent carboxylic acid residue or a trivalent carboxylic acid residue, m represents a number of 1 or 2, and n represents an integer of 1 to 20. The photosensitive resin composition for a light-shielding film according to claim 1 or claim 2, wherein the mass ratio (A) / (B) of the component (A) to the component (B) is 50/50 to 90/10, with respect to 100 parts by mass of the total of the (A) component and the (B) component, the (C) component is 2 to 30 parts by mass and the (D) component is 1 to 20 parts by mass. The solid content containing the component which becomes the solid content by the photocuring of the photosensitive resin composition for light-shielding films contains (E) component of 40 mass%-70 mass%. The photosensitive resin composition for a light-shielding film according to item 1 or 2 of the scope of application for a patent, wherein the (E) component is carbon black. A display substrate comprising a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or lower, wherein the light-shielding film contains the following components (A) to (E) as an essential component A photosensitive resin composition for a light-shielding film is hardened, (A) a polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate acid adduct; (B) having at least three Photopolymerizable monomer with ethylenically unsaturated bonds; (C) oxime ester polymerization initiator; (D) azo polymerization initiator; and (E) selected from the group consisting of a black organic pigment, a mixed color organic pigment, and a light-shielding material More than one shading component in the group. A method for manufacturing a display substrate, which is a method for manufacturing a display substrate including a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or less, characterized in that it contains the following components (A) to (E) as required The photosensitive resin composition for a light-shielding film of a component is coated on a substrate, exposed through a mask, unexposed portions are removed by development, and then heated at 160 ° C or lower to form a light-shielding film having a predetermined pattern. (A) having (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds in the structure of an epoxy (meth) acrylate acid adduct containing a polymerizable unsaturated group; (C) an oxime ester (D) an azo-based polymerization initiator; and (E) one or more light-shielding components selected from the group consisting of a black organic pigment, a mixed-color organic pigment, and a light-shielding material.