JP6758070B2 - A method for manufacturing 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, and a display substrate. - Google Patents

Description

The present invention relates to a photosensitive resin composition for a light-shielding film, a display substrate provided with a light-shielding film cured thereof, and a method for manufacturing a display substrate. The present invention relates to a photosensitive resin composition for a light-shielding film suitable for forming a light-shielding film, a display substrate provided with a light-shielding film as a cured film thereof on the substrate, and a method for manufacturing the display substrate.

Recently, for the purpose of making devices flexible and one-chip, for example, a light-shielding film (light-shielding pattern) is directly applied to a plastic substrate (plastic film, resin film) such as PET (polyethylene terephthalate) or PEN (polyethylene naphthalate). ), Or a light-shielding film is directly formed on a device provided with an organic EL, an organic TFT, or the like on a glass substrate or a silicon wafer. However, these have low heat-resistant temperatures of the plastic substrate itself and heat-resistant temperatures of the device, and in general, the heat resistance is often only about 160 ° C. at most. Therefore, when forming a light-shielding film on a plastic substrate or device, the film strength becomes insufficient at a heat firing temperature of 160 ° C. or lower, and in subsequent subsequent steps (for example, each RGB resist coating or alkali resistance), the film of the coating film. There is a problem that problems such as reduction, surface roughness, and pattern peeling occur.

Therefore, for example, Japanese Patent Application Laid-Open No. 2003-15288 (Patent Document 1) describes a photosensitive resin composition containing an alkali-soluble resin of an acrylic copolymer as a base and a thermal polymerization initiator in addition to a photopolymerization initiator. A substrate used, coated, exposed, patterned, and heat-baked at 150 ° C. is disclosed. Although the residue and adhesion to the substrate (peeling test) are ensured, the pattern line width, development margin, and so on. There is no description of reliability (solvent resistance, alkali resistance), etc., and these are not yet sufficient.

Japanese Unexamined Patent Publication No. 2003-15288

The present invention has been made in view of the above problems, and an object of the present invention is that it is suitable for forming a light-shielding film on a plastic substrate or device having a heat resistance of at most 160 ° C. It is an object of the present invention to provide a photosensitive resin composition for a light-shielding film capable of obtaining a light-shielding film having excellent solvent resistance and alkali resistance even for these low plastic substrates and devices. Then, the present invention provides 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 producing the same.

Therefore, the present inventors can obtain a light-shielding film having excellent solvent resistance and alkali resistance while obtaining good development adhesion and pattern linearity by thermosetting at 160 ° C. or lower. As a result of diligent studies on the composition, a predetermined polymerizable unsaturated group-containing alkali-soluble resin, a photopolymerizable monomer, a light-shielding component, and a solvent are contained, and two specific polymerization initiators are combined to form the above-mentioned composition. The present invention has been completed by finding that such a problem can be solved.
That is, the gist of the present invention is as follows.

（式中、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ_５は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、−Ｓｉ（ＣＨ_３）_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、フルオレン−９，９−ジイル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ_１及びＹ_２は、それぞれ独立して水素原子又は−ＯＣ−Ｚ−（ＣＯＯＨ）_ｍ（但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１又は２の数を表す）を表し、ｎは１〜２０の整数を表す。）
(５) 前記（Ａ）成分と（Ｂ）成分との質量割合（Ａ）／（Ｂ）が５０／５０〜９０／１０であり、前記（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、（Ｃ）成分が２〜３０質量部であると共に（Ｄ）成分が１〜２０質量部であり、遮光膜用感光性樹脂組成物の光硬化により固形分となる成分を含めた固形分中に（Ｅ）成分が４０〜７０質量％含まれる（３）又は（４）に記載の遮光膜用感光性樹脂組成物。
(６) （Ｅ）成分がカーボンブラックである（３）〜（５）のいずれかに記載の遮光膜用感光性樹脂組成物。 ( 1 ) A display substrate provided with a light-shielding film on a substrate having a heat resistant temperature of 160 ° C. or lower.
The light-shielding film contains the following components (A) to (E).
(A) A polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate adduct,
(B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) Oxime ester-based polymerization initiator,
(D) Azo-based polymerization initiator,
And (E) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials.
A substrate for a display, which is obtained by curing a photosensitive resin composition for a light-shielding film containing the above as an essential component.
( 2 ) A method for manufacturing a display substrate having a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or lower.
The following components (A) to (E),
(A) A polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate adduct,
(B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) Oxime ester-based polymerization initiator,
(D) Azo-based polymerization initiator,
And (E) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials.
A photosensitive resin composition for a light-shielding film containing as an essential component is applied onto a substrate, exposed through a photomask, unexposed areas are removed by development, and then heated at 160 ° C. or lower to give a predetermined value. A method for manufacturing a display substrate, which comprises forming a light-shielding film having a pattern.
( 3 ) The following components (A) to (E),
(A) A polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate adduct,
(B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) Oxime ester-based polymerization initiator,
(D) 1,1'-azobis (1-acetoxy-1-phenylethane) , which is an azo-based polymerization initiator,
And (E) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials.
A photosensitive resin composition for a light-shielding film, which comprises the above as an essential component.
( 4 ) The polymerizable unsaturated group-containing alkali-soluble resin of the component (A) is the photosensitive resin composition for a light-shielding film according to (3) represented by the following general formula (II).

(In the formula, 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 R ₅ is a hydrogen atom or a methyl group. , A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O- represents a 9,9-diyl group, or a direct bond, X represents a tetravalent carboxylic acid residue, _{Y 1} and _{Y 2} are each independently a hydrogen atom or a -OC-Z- _{(COOH) m} (However, Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20.)
( 5 ) The mass ratio (A) / (B) of the component (A) and the component (B) is 50/50 to 90/10, and the total of the component (A) and the component (B) is 100 parts by mass. On the other hand, the component (C) is 2 to 30 parts by mass and the component (D) is 1 to 20 parts by mass, and a component that becomes a solid content by photocuring of the photosensitive resin composition for a light-shielding film is included. The photosensitive resin composition for a light-shielding film according to (3) or (4), wherein the component (E) is contained in an amount of 40 to 70% by mass in the solid content.
( 6 ) The photosensitive resin composition for a light-shielding film according to any one of (3) to (5), wherein the component (E) is carbon black.

The photosensitive resin composition for a light-shielding film of the present invention has development adhesion at a line width of 5 to 15 μm, particularly 10 μm or less, even if it does not include a step of thermosetting at a temperature exceeding 160 ° C. in the process of producing the light-shielding film. It is possible to form a light-shielding film (light-shielding pattern) having excellent linearity and solvent resistance. Therefore, a light-shielding film is formed on a resin film such as PET or PEN having a heat resistant temperature of 160 ° C. or less, or a device provided with an organic EL or an organic TFT formed on a glass substrate or a silicon wafer. It is possible to obtain a display substrate having a light-shielding film having the above-mentioned characteristics.

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 polymerization initiator. By using a photosensitive resin composition containing a light-shielding component as an essential component, a desired light-shielding film is formed on a substrate having low heat resistance such as a heat-resistant temperature of 160 ° C. or less, and a display having various functions is provided. Can be used as a substrate.

Hereinafter, the present invention will be described in detail.
First, each component of the photosensitive resin composition for a light-shielding film of the present invention will be described.

但し、一般式（Ｉ）において、Ｒ₁、Ｒ₂、Ｒ_３及びＲ_４は、独立に水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示し、Ａは、‐CO‐、−SO₂−、‐C(CF₃)₂−、-Si(CH₃)₂‐、-CH₂‐、-C(CH₃)₂‐、-O-、フルオレン-9,9-ジイル基又は直結合を示し、ｌは０〜１０の平均値である。 The polymerizable unsaturated group-containing alkali-soluble resin of the component (A) in the present invention has the structure of an epoxy (meth) acrylic acid adduct, and more specifically, a compound having two or more epoxy groups and (meth). ) A compound obtained by reacting a reaction product with acrylic acid (which means "acrylic acid and / or methacrylic acid") with a polyvalent carboxylic acid or an anhydride thereof. Explaining in detail using a preferred example, the epoxy compound represented by the following general formula (I) is reacted with (meth) acrylic acid, and the obtained compound having a hydroxy group is treated with (a) dicarboxylic acid or tricarboxylic acid. Alternatively, it is an epoxy (meth) acrylate acid adduct obtained by reacting an acid anhydride thereof and (b) tetracarboxylic acid or an acid dianhydride thereof. The epoxy compound represented by the general formula (I) means an epoxy compound obtained by reacting bisphenols with epihalohydrin or an equivalent thereof. Since the component (A) has both a polymerizable unsaturated double bond and a carboxyl group, it gives the photosensitive resin composition excellent photocurability, good developability, and patterning properties, and improves the physical properties of the light-shielding film.

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 is -CO-. , -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, Fluoren-9,9-diyl group Alternatively, it indicates a direct bond, and l is an average value of 0 to 10.

Examples of bisphenols that give 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) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoro Propane, 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'-biphenol, 3,3'- Examples include biphenol. Among these, bisphenols that give 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 the general formula (I) for inducing the alkali-soluble resin of (A) is an epoxy compound having two glycidyl ether groups obtained by reacting the above bisphenols with epichlorohydrin. In this reaction, generally accompanied by oligomerization of the diglycidyl ether compound, l usually has an average value of 0 to 10 (not necessarily an integer) because a plurality of values are mixed, but a preferable average value of l is obtained. Is 0 to 3. If the average value of l exceeds the upper limit, the viscosity of the composition becomes too large when a photosensitive resin composition using an alkali-soluble resin synthesized by using the epoxy compound is prepared, and the coating cannot be performed successfully. Or, the alkali solubility cannot be sufficiently imparted and the alkali developability becomes very poor.

As the (a) dicarboxylic acid or tricarboxylic acid or its acid anhydride used for the epoxy (meth) acrylate acid adduct, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride or the alicyclic dicarboxylic acid or tricarboxylic acid is used. An acid or an acid anhydride thereof, an aromatic dicarboxylic acid or a tricarboxylic acid or an acid anhydride thereof is used. Here, examples of the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or its acid anhydride include succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralinic acid, malonic acid, and glutaric acid. There are compounds such as citric acid, tartaric acid, oxoglutaric acid, pimeric acid, sebacic acid, suberic acid, diglycolic acid or acid anhydrides thereof, and dicarboxylic acid or tricarboxylic acid having an arbitrary substituent introduced therein or acid anhydride thereof. It may be a thing. Examples of the alicyclic dicarboxylic acid or tricarboxylic acid or its acid anhydride include compounds such as cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and norbornandicarboxylic acid, or acid anhydrides thereof. There may be a dicarboxylic acid or a tricarboxylic acid into which an arbitrary substituent has been introduced, or an acid anhydride thereof. Further, examples of the aromatic dicarboxylic acid or tricarboxylic acid or its acid anhydride include compounds such as phthalic acid, isophthalic acid and trimellitic acid or acid anhydrides thereof, and further, a dicarboxylic acid into which an arbitrary substituent is introduced. Alternatively, it may be a tricarboxylic acid or an acid anhydride thereof.

Further, as the (b) tetracarboxylic acid or its acid dianhydride used for the epoxy (meth) acrylate acid adduct, the chain hydrocarbon tetracarboxylic acid or its acid dianhydride or the alicyclic tetracarboxylic acid or The acid dianhydride, or the aromatic polyvalent carboxylic acid or the acid dianhydride thereof is used. Here, examples of the chain hydrocarbon tetracarboxylic acid or its acid dianhydride include compounds such as butanetetracarboxylic acid, pentantetracarboxylic acid, and hexanetetracarboxylic acid, or acid dianhydrides thereof, and further optionally. It may be a tetracarboxylic acid into which the substituent of the above is introduced or an acid dianhydride thereof. Examples of the alicyclic tetracarboxylic acid or its acid dianhydride include compounds such as cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptantetracarboxylic acid and norbornanetetracarboxylic acid. There is the acid dianhydride, and further, it may be a tetracarboxylic acid in which an arbitrary substituent is introduced or an acid dianhydride thereof. Further, examples of the aromatic tetracarboxylic acid and its acid dianhydride include compounds such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid and biphenylethertetracarboxylic acid, or acid dianhydrides thereof. Further, a tetracarboxylic acid having an arbitrary substituent introduced therein or an acid dianhydride thereof may be used.

The molar ratio (a) / (b) of (a) dicarboxylic acid or tricarboxylic acid or acid anhydride thereof used in the epoxy (meth) acrylate acid adduct to (b) tetracarboxylic acid or acid dianhydride thereof is , 0.01 to 10.0, 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 for obtaining the photosensitive resin composition having high light-shielding and high resistance of the present invention and good photopatterning property cannot be obtained. Therefore, it is not preferable. The smaller the molar ratio (a) / (b), the larger the molecular weight, and the less alkaline the solubility tends to be.

（式中、Ｒ _１ 、Ｒ _２ 、Ｒ _３ 及びＲ _４ は、それぞれ独立して水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を表し、Ｒ _５ は、水素原子又はメチル基を表し、Ａは、−ＣＯ−、−ＳＯ _２ −、−Ｃ（ＣＦ _３ ） _２ −、−Ｓｉ（ＣＨ _３ ） _２ −、−ＣＨ _２ −、−Ｃ（ＣＨ _３ ） _２ −、−Ｏ−、フルオレン−９，９−ジイル基又は直結合を表し、Ｘは４価のカルボン酸残基を表し、Ｙ _１ 及びＹ _２ は、それぞれ独立して水素原子又は−ＯＣ−Ｚ−（ＣＯＯＨ） _ｍ （但し、Ｚは２価又は３価カルボン酸残基を表し、ｍは１又は２の数を表す）を表し、ｎは１〜２０の整数を表す。） The epoxy (meth) acrylate adduct can be produced by the above-mentioned steps by a known method, for example, the method described in JP-A-8-278629, JP-A-2008-9401, and the like. First, as a method of reacting the epoxy compound of the general formula (I) with (meth) acrylic acid, for example, an equimolar (meth) acrylic acid with an epoxy group of the epoxy compound is added to a solvent, and a catalyst (triethylbenzyl) is added. In the presence of (ammonium chloride, 2,6-diisobutylphenol, etc.), there is a method of heating and stirring at 90 to 120 ° C. while blowing air to react. Next, as a method of reacting the acid anhydride with the hydroxyl group of the epoxy acrylate compound which is the reaction product, a predetermined amount of the epoxy acrylate compound, the acid dianhydride and the acid monoanhydride is added to the solvent, and a catalyst (odor) is added. There is a method of reacting by heating and stirring at 90 to 130 ° C. in the presence of tetraethylammonium oxide, triphenylphosphine, etc.). In this way, the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) in the present invention, preferably the polymerizable unsaturated group-containing alkali-soluble resin represented by the following general formula (II) can be obtained. ..

(In the formula, 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 R ₅ is a hydrogen atom or a methyl group. , A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O- represents a 9,9-diyl group, or a direct bond, X represents a tetravalent carboxylic acid residue, _{Y 1} and _{Y 2} are each independently a hydrogen atom or a -OC-Z- _{(COOH) m} (However, Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20.)

The weight average molecular weight (Mw) of the polymerizable unsaturated group-containing alkali-soluble resin (A) is preferably in the range of 2000 to 10000, and more preferably between 3000 and 7000. If the weight average molecular weight (Mw) is less than 2000, the pattern adhesion during development of the photosensitive resin composition using (A) cannot be maintained, pattern peeling occurs, and the weight average molecular weight (Mw) is 10,000. If it exceeds, the development residue and the residual film of the unexposed portion are likely to remain. Further, (A) preferably has an acid value in the range of 80 to 120 mgKOH / g. If this value is less than 80 mgKOH / g, a residue is likely to remain during alkaline development of the photosensitive resin composition using (A), and if it exceeds 120 mgKOH / g, the alkali to the photosensitive resin composition using (A) is likely to remain. Both are not preferable because the developer penetrates too quickly and peeling development occurs. As for the polymerizable unsaturated group-containing alkali-soluble resin (A), it is possible to use only one of them or a mixture of two or more of them.

Next, (B) examples of the photopolymerizable monomer having at least three ethylenically unsaturated bonds include trimethyl propantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, and pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Sorbitol hexa (meth) acrylate, alkylene oxide-modified hexa (meth) acrylate of phosphazene, caprolactone-modified dipentaerythritol hexa (meth) acrylate and other (meth) acrylic acid esters, dendrimer-type polyfunctional acrylates, hyperbranched poly Functional acrylates and the like can be mentioned, and one or more of these can be used. In addition, (B) a photopolymerizable monomer having at least three ethylenically unsaturated bonds does not have a free carboxy group. In the present invention, a trifunctional or higher photopolymerizable monomer is used in order to obtain a sufficient crosslink density only by heat treatment at 160 ° C. or lower.

The blending ratio of the component (A) and the component (B) is preferably 50/50 to 90/10 in terms of mass ratio (A) / (B), preferably 60/40 to 80/20. Is good. If the compounding ratio of the component (A) is less than 50/50 in (A) / (B), the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed portion, so that alkali development There is a problem that the solubility in a liquid is lowered and the pattern edge is not sharpened, and when the ratio of (A) / (B) is more than 90/10, the ratio of photoreactive functional groups in the resin is high. The formed pattern is formed because the crosslinked structure is not sufficiently formed, and the acid value of the coating film in the exposed portion due to the resin component is too high and the solubility in the alkaline developer in the exposed portion is high. There is a risk that the line width will be narrower than the target line width, and that patterns will be easily missing.

Examples of the oxime ester-based polymerization initiator of the component (C) include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4). -(Phenylsulfanyl) phenyl) butane-1,2-dione-2-oxime-O-benzoate, 1-(4- (methylsulfanyl) phenyl) butane-1,2-dione-2-oxime-O-acetate , 1- (4- (methylsulfanyl) phenyl) butane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) carbazole-3-yl] etanone = O-acetyloxime, (9-Ethyl-6-nitrocarbazole-3-yl) [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone = O-acetyloxime, (8-{[(acetyloxy) imino) ] [2- (2,2,3,3-tetrafluoropropoxy) phenyl] methyl} -11- (2-ethylhexyl) -11H-benzo [a] carbazole-5-yl) (2,4,6-trimethyl) Phenyl) methanone, (2-methylphenyl) (7-nitro-9,9-dipropyl-9H-fluoren-2-yl)-, acetyloxime, etanone, 1- [7- (2-methylbenzoyl) -9, 9-dipropyl-9H-fluoren-2-yl]-,1- (O-acetyloxime), etanone, 1- (-9,9-dibutyl-7-nitro-9H-fluoren-2-yl)-, 1 -O-acetyloxime and the like can be mentioned. Further, two or more kinds of these oxime ester-based polymerization initiators can also be used.

The main function of the oxime ester-based polymerization initiator of the component (C) is to initiate photoradical polymerization, and the amount used is 2 to 30 based on a total of 100 parts by mass of the components (A) and (B). It is preferably parts by mass, preferably 5 to 25 parts by mass. When the compounding ratio of the component (C) is less than 2 parts by mass, the photopolymerization rate becomes slow and the sensitivity decreases, while when it exceeds 30 parts by mass, the sensitivity is too strong and the pattern line. The width becomes thicker than that of the pattern mask, and there is a possibility that a line width faithful to the mask cannot be reproduced, or the pattern edge is not sharpened.

Examples of the azo-based polymerization initiator of the component (D) include azobisisobutyronitrile (10-hour half-life temperature (toluene) (hereinafter T _1/2 ) 65 ° C.), 2,2'-azobis (2,4-). Dimethylvalonitrile) (T _1/2 51 ° C), dimethyl 2,2'-azobis (2-methylpropionate) (T _1/2 66 ° C), dimethyl 1,1'-azobis (1-cyclohexanecarboxylate) ) (T _1/2 73 ° C), 1,1'-azobis (cyclohexane-1-carbonitrile) (T _1/2 88 ° C), 1,1'-azobis (1-acetoxy-1-phenylethane) ( T _1/2 61 ° C.), dimethyl 2,2'-azobisisobutyrate (T _1/2 67 ° C.), and the like.

The function of the azo-based polymerization initiator of the component (D) is mainly to improve the thermal radical polymerization property of the photosensitive resin composition, and in particular, to cure the hardness of the pattern formed by thermal polymerization during post-baking after exposure and development. The purpose is to improve the physical properties of things. Therefore, it is necessary to add an appropriate 10-hour half-life temperature (T _1/2 ) in an appropriate amount depending on post-baking conditions and the like. The preferred 10-hour half-life temperature is 50 to 80 ° C., and the amount used is preferably 1 to 20 parts by mass based on a total of 100 parts by mass of the components (A) and (B), preferably 2. It is preferably ~ 15 parts by mass.

The component (E) is a light-shielding component selected from black organic pigments, mixed-color organic pigments, and light-shielding materials, 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, lactam black and the like. Examples of the mixed color organic pigment include those obtained by mixing two or more kinds of pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like to make a pseudo black color. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, titanium black and the like. Two or more types of light-shielding components can be appropriately selected and used, but carbon black is particularly preferable in that it has good light-shielding properties, surface smoothness, dispersion stability, and compatibility with resins. Further, as the carbon black to be used, a carbon black whose surface is coated with a dye, resin or the like is suitable for making a cured product having high resistance.

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

The light-shielding component (E) is preferably dispersed in a solvent (F) together with a dispersant (G) to prepare a light-shielding dispersion, and then blended as a photosensitive resin composition for a light-shielding film. Here, as the solvent to be dispersed, any solvent listed in the above component (F) can be used, and for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and the like are preferably used. The blending ratio of the light-shielding component (E) that forms the light-shielding dispersion is often used in the range of 40 to 70% by mass with respect to the total solid content of the photosensitive resin composition for a light-shielding film of the present invention. , 40-60% by mass is particularly preferable. If it is less than 40% by mass, the light-shielding property is not sufficient for high light-shielding. If it exceeds 70% by mass, the content of the photosensitive resin as the original binder decreases, which causes an unfavorable problem that the developing characteristics are impaired and the film forming ability is impaired. The total solid content of the photosensitive resin composition for a light-shielding film includes a component in which the photosensitive resin composition for a light-shielding film becomes a solid content by photocuring.

As the dispersant (G) to be used, known dispersants such as various polymer dispersants can be used. As a specific example of the dispersant, known compounds conventionally used for pigment dispersion (compounds commercially available under the names of dispersants, dispersion wetting agents, dispersion accelerators, etc.) may be used without particular limitation. However, for example, a cationic polymer-based dispersant, an anionic polymer-based dispersant, a nonionic polymer-based dispersant, a pigment derivative-type dispersant (dispersion aid), and the like can be mentioned. In particular, it has a cationic functional group such as an imidazolyl group, a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group as an adsorption point to a pigment, has an amine value of 1 to 100 mgKOH / g, and has a number average molecular weight. A cationic polymer dispersant having a value in the range of 10 to 100,000 is suitable. The blending amount of this dispersant is preferably 1 to 30% by mass, preferably 2 to 25% by mass, based on the light-shielding component.

Further, when preparing the light-shielding dispersion, a photosensitive resin composition for a light-shielding film is prepared by co-dispersing a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) in addition to the above-mentioned dispersant. Then, it is possible to obtain a photosensitive resin composition which makes it easy to maintain high exposure sensitivity, has good adhesion during development, and is less likely to cause a problem of residue. At that time, the blending amount of the component (A) is preferably 2 to 20% by mass, more preferably 5 to 15% by mass in the light-shielding dispersion. If the component (A) is less than 2% by mass, the effects of covariance, sensitivity improvement, adhesion improvement, and residue reduction cannot be obtained. Further, if it exceeds 20% by mass, the viscosity of the light-shielding dispersion liquid is high, particularly when the content of the light-shielding material is large, and it becomes difficult or very time-consuming to uniformly disperse the light-shielding dispersion, resulting in high resistance. It becomes difficult to obtain a photosensitive resin composition for obtaining a coating film. Then, the obtained light-shielding dispersion is mixed with the component (A), the component (B), the component (C), and the component (D), and the component (F) is added as necessary to meet the film forming conditions. By adjusting the viscosity to an appropriate level, a photosensitive resin composition for a light-shielding film can be obtained.

In addition, the photosensitive resin composition of the present invention contains, if necessary, polymerization initiators other than oxime ester-based and azo-based, chain transfer agents, sensitizers, non-photosensitive resins, curing accelerators, antioxidants, etc. Additives such as plasticizers, fillers, leveling agents, defoaming agents, coupling agents, surfactants, color adjusting pigments and dyes can be blended. Examples of polymerization initiators other than oxime esters and azo compounds include acetophenones, benzophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, benzoin ethers, biimidazole compounds, and halomethyldiazole compounds. , Halomethyl-s-triazine compounds and the like, and as the chain transfer agent and sensitizer, sulfur atom-containing compounds are generally used, and mercapto compounds, disulfide compounds and the like can be mentioned. , 1,4-Bis (3-mercaptobutyryloxy) butane and other aliphatic polyfunctional thiols can be preferably exemplified. Examples of the non-photosensitive resin include bisphenol type epoxy resins, novolak type epoxy resins, alicyclic epoxy resins, epoxy silicone resins and the like, and examples of antioxidants include hindered phenolic antioxidants. Phosphorus-based antioxidants and the like can be mentioned, examples of the plasticizer can be dibutylphthalate, dioctylphthalate, tricredyl phosphate and the like, and examples of the filler can be glass fiber, silica, mica, alumina and the like. Examples of the defoaming agent and the leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and the like, and examples of the coupling agent include 3- (glycidyloxy) propyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane. Examples thereof include silane coupling agents such as 3-ureidopropyltriethoxysilane.

The photosensitive resin composition of the present invention preferably contains the above components (A) to (F) as main components. It is desirable that the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing) contains 80% by mass, preferably 90% by mass or more of the components (A) to (E) in total. The amount of the solvent (F) varies depending on the target viscosity, but it is preferable that the solvent is contained in the photosensitive resin composition in the range of 70 to 90% by mass.

As a method for forming a light-shielding film using the photosensitive resin composition for a light-shielding film in the present invention, there are the following photolithography methods. First, the photosensitive resin composition is applied onto a plastic substrate or device, and then the solvent is dried (prebaked), and then the film thus obtained is irradiated with ultraviolet rays through a photomask to cure the exposed portion. Further, a method of forming a pattern by elution of an unexposed portion with an alkaline aqueous solution and further performing post-baking (heat firing) as post-curing can be mentioned.

Examples of the substrate on which the photosensitive resin composition of the present invention is applied include resin films (plastic substrates) such as PET and PEN having a heat resistant temperature of 160 ° C. or lower. Here, the heat-resistant temperature is a temperature at which problems such as deformation do not occur even if the substrate is exposed in a processing process such as pattern formation of a light-shielding film on the substrate, and for a resin film, it depends on the degree of stretching treatment. It will vary, but at least it must not exceed the glass transition temperature (Tg). Further, a substrate in which electrodes such as ITO and gold are vapor-deposited or patterned on a resin film can also be exemplified.

In addition, as another example of the substrate to which the photosensitive resin composition of the present invention is applied, a thin film having high heat resistance but low heat resistance is formed on the substrate such as a glass substrate or a silicon wafer. Also included. Specific examples include devices in which an organic EL (OLED) or an organic thin film transistor (TFT) is formed on a glass or silicon wafer. The heat-resistant temperature of a substrate having low heat resistance, such as a resin film or a device, which is the subject of the present invention, varies depending on the type of resin and the device, but can be generally said to be 100 to 160 ° C.

As a method of applying the solution of the photosensitive resin composition on these substrates, any of a known solution dipping method, a spray method, a roller coater machine, a land coater machine, a slit coater machine, a spinner machine, and the like can be used. Method can also be adopted. By these methods, a film is formed by applying to a desired thickness and then removing the solvent (prebaking). Pre-baking is performed by heating in an oven, a hot plate, or the like. The heating temperature and heating time in the prebake are appropriately selected according to the solvent used, and are carried out at a temperature of, for example, 60 to 110 ° C. for 1 to 3 minutes.

The exposure performed after the prebaking is performed by an ultraviolet exposure apparatus, and by exposing through a photomask, only the resist of the portion corresponding to the pattern is exposed. The exposure apparatus 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, or a far-ultraviolet lamp to photocure the photosensitive resin composition in the coating film.

Alkaline development after exposure is performed for the purpose of removing the resist in the unexposed portion, and this development forms a desired pattern. Examples of the developing solution suitable for this alkaline development include an aqueous solution of an alkali metal or an alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like, and in particular, sodium carbonate, potassium carbonate, and lithium carbonate. It is preferable to develop at a temperature of 23 to 28 ° C. using a weak alkaline aqueous solution containing 0.05 to 3% by mass of carbonate such as, and to obtain a fine image using a commercially available developer or ultrasonic washing machine. Can be formed precisely.

After development, heat treatment (post-baking) is preferably performed at a temperature of 100 to 160 ° C. and conditions of 20 to 60 minutes. This post-baking is performed for the purpose of enhancing the adhesion between the patterned light-shielding film and the substrate. This is done by heating in an oven, hot plate, etc., similar to prebaking. The patterned light-shielding film of the present invention is formed through each step by the above photolithography method.

As described above, the photosensitive resin composition of the present invention can be suitably used for forming a light-shielding film on a substrate having a low heat-resistant temperature by operations such as exposure and alkaline development. It is particularly suitable when even a fine light-shielding film pattern is required. Specifically, when a substrate having a low heat-resistant temperature is used, a black matrix or partition material for color filters and organic EL pixel formation (for cases where RGB is formed by an inkjet method, etc.), a light-shielding film, and light-shielding for a touch panel are used. It is useful for forming a film or the like, and these substrates with a light-shielding film can be used for a display device such as a liquid crystal or an organic EL or for a member of a photographing element (that is, these are collectively referred to as a display substrate). is there.

Hereinafter, embodiments of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.

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

[Solid content concentration]
A glass filter [weight: W ₀ (g)] is impregnated with 1 g of the resin solution obtained in the synthesis example, weighed [W ₁ (g)], and heated at 160 ° C. for 2 hr, and then weight [W ₂ ( g)] was obtained from the following equation.
Solid content concentration (% by weight) = 100 x (W _2- W ₀ ) / (W _1- W ₀ )

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

[Molecular weight]
Gel Permeation Chromatography (GPC) [Product name HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper- Measured with H5000 (1 bottle) [manufactured by Tosoh Corporation], temperature: 40 ° C., speed: 0.6 ml / min], and measured with standard polystyrene [PS-oligomer kit manufactured by Tosoh Corporation], weight average molecular weight ( Mw) was calculated.

The abbreviations used in the synthesis example are as follows.
BPFE: A reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyl oxylane. In the compounds of formula (I), A is _{9,9-diyl, R 1, R 2, R} 3, R 4 is a hydrogen compound.
AA: Acrylic acid
BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
MAA: Methacrylic acid
MMA: Methyl methacrylate
CHMA: Cyclohexyl methacrylate
GMA: Glycydyl 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]
BPFE 114.4 g (0.23 mol), AA 33.2 g (0.46 mol), PGMEA 157 g and TEAB 0.48 g were placed in a 500 ml four-necked flask with a return condenser, and the reaction was carried out by stirring at 100 to 105 ° C for 20 hours. I let you. Next, 35.3 g (0.12 mol) of BPDA and 18.3 g (0.12 mol) of THPA were charged in a flask and stirred at 120 to 125 ° C. under heating 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 (solid content equivalent) was 103 mgKOH / g, and the Mw by GPC analysis was 3600.

[Synthesis Example 2]
Put MAA 51.7g (0.60mol), MMA 38.0g (0.38mol), CHMA 37.0g (0.22mol), AIBN5.91g, and DMDG 295g in a 1000ml four-necked flask with a nitrogen introduction tube and a reflux tube, 80 ~ Polymerization was carried out by stirring at 85 ° C. under a nitrogen stream for 8 hours. Further, 39.8 g (0.28 mol) of GMA, 1.44 g of TPP, and 0.055 g of DTBC were charged in the flask and stirred at 80 to 85 ° C. for 16 hours to obtain a polymerizable unsaturated group-containing (meth) acrylate resin (A) -2. It was. 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 by GPC analysis was 18080.

Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the production of the photosensitive resin composition for a light-shielding film and the cured product thereof, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the photosensitive resin composition for a light-shielding film and the cured product 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 above
(A) -2: Alkali-soluble resin solution obtained in Synthesis Example 2 above

(Photopolymerizable monomer)
(B) -1: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Toagosei Corporation, trade name Aronix M-405)
(B) -2: Trimethylolpropane triacrylate, (manufactured by Sartmer Japan Co., Ltd., trade name SR351S)
(B) -3: EO adduct diacrylate of bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd., trade name light acrylate BP-4EAL)

(Oxime ester polymerization initiator)
(C): Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime) (manufactured by BASF Japan, product name Irgacure OXE02) )

(Azo-based polymerization initiator, etc.)
(D) -1: 2,2-Azobisisobutyronitrile (trade name V-60 manufactured by Wako Pure Chemical Industries, Ltd.)
(D) -2: Dimethyl 2,2-azobis 2-methylpropionate) (Product name V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
(D) -3: 1,1'-azobis (1-acetoxy-1-phenylethane) (Product name: OTAZO-15, manufactured by Otsuka Chemical Co., Ltd.)
(D) -4: Benzoyl peroxide, (Product name: NOF BMT-K40)

(Light-shielding dispersion pigment)
(E): PGMEA dispersion liquid (solid content 29.75%) having a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 4.75% by mass.

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

(Silane coupling agent)
(H): S-510 (manufactured by JNC)

(Surfactant)
(I): Mega Fvck F475 (manufactured by DIC Corporation)

The above-mentioned compounding components were blended in the proportions shown in Table 1 to prepare photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4. All the numerical values in Table 1 represent parts by mass. Further, (F) -1 and (F) -2 are amounts that do not contain the solvent in (A) -1 and (A) -2 and the solvent in (E).

[Evaluation]
The evaluations described below were carried out using the photosensitive resin compositions for black resist of Examples 1 to 6 and Comparative Examples 1 to 4. The evaluation results are shown in Tables 2 and 3.

<Evaluation of development characteristics (pattern line width / pattern linearity)>
Each of the photosensitive resin compositions obtained above was applied to a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.2 μm, and at 90 ° C. Prebaked for 1 minute. After that, the exposure gap was adjusted to 100 μm, a negative photomask with line / space = 10 μm / 50 μm was placed on the dry coating film, and an ultrahigh pressure mercury lamp with an i-line illuminance of 30 mW / cm ² was used to generate 50 mJ / cm ² ultraviolet rays. Was irradiated, and a photocuring reaction of the photosensitive portion was carried out.

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

Pattern line width: A pattern line width with a 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, and if there is no peeling on the substrate or jaggedness of the pattern edge part, it is ○, if it is partially recognized, it is △, and it is recognized throughout. Was evaluated as x.
The pattern line width and the pattern linearity were evaluated in the case of BT + 10 seconds and the case of BT + 20 seconds.

<Evaluation of OD / μm>
Each of the photosensitive resin compositions obtained above was applied to a 125 mm × 125 mm glass substrate (Corning 1737) using a spin coater so that the film thickness after post-baking was 1.1 μm, and at 90 ° C. Prebaked for 1 minute. Then, the photocuring reaction was carried out by irradiating ultraviolet rays of 80 mJ / cm ² with an ultra-high pressure mercury lamp having an i-ray illuminance of 30 mW / cm ² without covering with a negative photomask.

Next, this exposed coated plate was developed with a shower pressure of 1 kgf / cm ² for 60 seconds using a 0.05% potassium hydroxide aqueous solution at 25 ° C., then washed with spray water at 5 kgf / cm ² pressure, and then hot air was washed. It was heat post-baked at 120 ° C. for 60 minutes using a dryer. The OD value of this coated plate was evaluated using a Macbeth transmission densitometer. Further, 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 defined as OD / μm.

<Evaluation of solvent resistance>
The solvent resistance of the formed coating film (light-shielding film) was evaluated using the coated plate (glass plate with a light-shielding film) prepared in the same manner as in the OD evaluation. The surface condition was observed by continuously rubbing with a waste cloth immersed in PGMEA or cyclohexanone (anone), and the number of times of rubbing when the coating film surface was melted or softened and scratched was recorded. When the number of times when any solvent was used was 20 times or more, the solvent resistance was evaluated as ◯, and when the number of times was less than 20, the solvent resistance was evaluated as ×.

<Stability over time>
With respect to the initial solution viscosity of the prepared photosensitive resin solution, the solution viscosity after being left at room temperature of 23 ° C. for 5 days was increased by 1.5 times or more of the initial solution viscosity, and less than 1.5 times was evaluated as 〇.

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 when post-baked at a low temperature of 120 ° C., and solvent resistance to PGMEA and anone is maintained. A light-shielding film pattern having sufficient properties can be formed, and storage stability as a photosensitive resin composition solution is also sufficient.
On the other hand, when a bifunctional monomer is used as the photopolymerizable monomer as in Comparative Example 1, the crosslink density of the cured film after post-baking cannot be sufficiently obtained, and the pattern linearity is obtained when the development time is slightly longer. Poor and solvent resistance is insufficient. If a peroxide-based polymerization initiator is used instead of the azo-based polymerization initiator for imparting thermal radical polymerization as in Comparative Example 2, the storage stability of the photosensitive resin composition solution is not sufficient. When the azo-based polymerization initiator is not added as in Comparative Example 3, sufficient solvent resistance cannot be obtained when the post-bake temperature is low. When an acrylic copolymer-based compound is used as the polymerizable unsaturated group-containing alkali-soluble resin instead of the compound of the general formula (II) as in Comparative Example 4, cross-linking does not proceed sufficiently at a low post-bake temperature. A pattern with sufficiently good linearity cannot be obtained, and solvent resistance is also insufficient.

The photosensitive resin composition for a light-shielding film in the present invention has development adhesion at a line width of 5 to 15 μm, particularly 10 μm or less, even if it does not include a step of thermosetting at a temperature exceeding 160 ° C. in the process of producing the light-shielding film. It is possible to form a light-shielding film (light-shielding pattern) having excellent linearity and solvent resistance. Therefore, the above characteristics are obtained for a resin film such as PET or PEN having a heat resistant temperature of 160 ° C. or lower, or a device having an organic EL or organic TFT on a glass substrate or a silicon wafer. It is possible to form a light-shielding film provided with.
That is, the photosensitive resin composition for a light-shielding film of the present invention heat-resistants a light-shielding film such as a black matrix, a partition material, and a column spacer having a light-shielding function, which are required for forming a color filter or an organic EL pixel, for example. It is suitable for providing on a substrate with a low temperature, or for providing a light-shielding film such as a frame (bezel) portion required for forming a touch panel, and these substrates with a light-shielding film (that is, a display substrate). ) Can be used in the manufacture of display devices such as liquid crystal and organic EL, and in the manufacture of solid-state photographing elements such as CMOS.

Claims (6)

A display substrate provided with a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or lower.
The light-shielding film contains the following components (A) to (E).
(A) A polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate adduct,
(B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) Oxime ester-based polymerization initiator,
(D) Azo-based polymerization initiator,
And (E) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials.
A substrate for a display, which is obtained by curing a photosensitive resin composition for a light-shielding film containing the above as an essential component. A method for manufacturing a display substrate having a light-shielding film on a substrate having a heat-resistant temperature of 160 ° C. or lower.
The following components (A) to (E),
(A) A polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate adduct,
(B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) Oxime ester-based polymerization initiator,
(D) Azo-based polymerization initiator,
And (E) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials.
A photosensitive resin composition for a light-shielding film containing as an essential component is applied onto a substrate, exposed through a photomask, unexposed areas are removed by development, and then heated at 160 ° C. or lower to give a predetermined value. A method for manufacturing a display substrate, which comprises forming a light-shielding film having a pattern. The following components (A) to (E),
(A) A polymerizable unsaturated group-containing alkali-soluble resin having a structure of an epoxy (meth) acrylate adduct,
(B) A photopolymerizable monomer having at least three ethylenically unsaturated bonds,
(C) Oxime ester-based polymerization initiator,
(D) 1,1'-azobis (1-acetoxy-1-phenylethane) , which is an azo-based polymerization initiator,
And (E) one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments, and light-shielding materials.
A photosensitive resin composition for a light-shielding film, which comprises the above as an essential component. The photosensitive resin composition for a light-shielding film according to claim 3 , 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 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ is a hydrogen atom or a methyl group. , A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O- represents a 9,9-diyl group, or a direct bond, X represents a tetravalent carboxylic acid residue, _{Y 1} and _{Y 2} are each independently a hydrogen atom or a -OC-Z- _{(COOH) m} (However, Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20.) The mass ratio (A) / (B) of the component (A) and the component (B) is 50/50 to 90/10, and the mass ratio of the component (A) and the component (B) is 100 parts by mass in total. , The component (C) is 2 to 30 parts by mass and the component (D) is 1 to 20 parts by mass, and the solid content including the component which becomes a solid content by photocuring of the photosensitive resin composition for a light-shielding film The photosensitive resin composition for a light-shielding film according to claim 3 or 4 , wherein the component (E) is contained in an amount of 40 to 70% by mass. The photosensitive resin composition for a light-shielding film according to any one of claims 3 to 5 , wherein the component (E) is carbon black.