Photosensitive resin composition, cured film obtained by curing the photosensitive resin composition, substrate with cured film, and method for producing substrate with cured film

Abstract

To provide a photosensitive resin composition from which a resin film pattern can be formed that is excellent in development adhesiveness and linearity even when a substrate having low heat resistance is used, and also excellent in solvent resistance, alkali resistance and the like.SOLUTION: The photosensitive resin composition of the present invention is to be used to form a cured film on a substrate having a heat-resistant temperature of 140°C or lower, and the composition comprises (A) an unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) an epoxy compound having at least two 3,4-epoxycyclohexyl groups, (D) a photopolymerization initiator, and (E) a solvent. The content of the (C) component is 5 to 17 mass% with respect to the whole mass of the solid content.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, a substrate with a cured film, and a method for producing a substrate with a cured film. [Background technology]

[0002] In recent years, with the aim of making devices more flexible and single-chip, there has been a demand for the ability to directly form cured film (transparent insulating film, etc.) patterns, colored film patterns, and light-shielding film patterns on plastic substrates (plastic films, resin films) such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate), as well as the ability to directly form cured film patterns, colored film patterns, and light-shielding film patterns on substrates with organic devices such as organic electroluminescence (EL) and organic thin-film transistors (TFTs) on glass substrates or silicon wafers.

[0003] However, since the above-mentioned plastic substrates and substrates with organic devices have low heat resistance of 140°C or less, when a resin film pattern, a colored film pattern, and a light-shielding film pattern are directly formed on a plastic substrate or a substrate with an organic device at a low baking temperature of 140°C or less using a conventional photosensitive resin composition, the film strength of the formed pattern becomes insufficient, and problems arise in subsequent processes (such as development processing) whereby problems such as film loss of the coating film, surface roughness, and pattern peeling occur.

[0004] Therefore, photosensitive resin compositions that can be used on substrates with low heat resistance have been studied. For example, Patent Document 1 discloses a radiation-sensitive composition containing an alkali-soluble resin of an acrylic copolymer, a photopolymerization initiator, and a thermal polymerization initiator. It is said that the radiation-sensitive composition can form a color filter that has sufficient adhesion to the substrate even when baked at a low temperature (100 to 140°C) that does not cause yellowing, because it contains a photopolymerization initiator and a thermal polymerization initiator. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2003-15288 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, according to the findings of the present inventors, the radiation-sensitive composition described in Patent Document 1 does not provide desired development characteristics (e.g., pattern line width, pattern linearity) and solvent resistance, although it has adhesion to a substrate.

[0007] The present invention has been made in consideration of the above points, and has an object to provide a photosensitive resin composition capable of forming a resin film pattern that is excellent in development adhesion and linearity and also in solvent resistance, alkali resistance, etc., even when a substrate having low heat resistance is used, a cured film obtained by curing the photosensitive resin composition, a substrate with a cured film, and a method for manufacturing a substrate with a cured film. [Means for solving the problem]

[0008] The photosensitive resin composition of the present invention is a photosensitive resin composition used for forming a cured film on a substrate having a heat resistance temperature of 140°C or less, and contains (A) an unsaturated group-containing alkali-soluble resin, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) an epoxy compound having two or more 3,4-epoxycyclohexyl groups, (D) a photopolymerization initiator, and (E) a solvent, and the mass of the component (C) is 5 to 17 mass% based on the total mass of the solid contents.

[0009] The cured film of the present invention is obtained by curing the above-mentioned photosensitive resin composition.

[0010] The substrate with a cured film of the present invention has the above-mentioned cured film.

[0011] The method for producing a substrate with a cured film of the present invention is a method for producing a substrate with a cured film by forming a cured film pattern on a substrate having a heat resistance temperature of 140°C or less, in which the photosensitive resin composition is applied onto the substrate, exposed through a photomask, and developed to remove the unexposed areas, and then heated at 140°C or less to form a cured film pattern. Effect of the Invention

[0012] According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a resin film pattern that is excellent in development adhesion and linearity and also in solvent resistance, alkali resistance, etc., even when a substrate having low heat resistance is used, a cured film obtained by curing the photosensitive resin composition, a substrate with a cured film, and a method for producing a substrate with a cured film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, an embodiment of the present invention will be described, but the present invention is not limited to the following embodiment. In addition, in the present invention, when the first decimal place of the content of each component is 0, the notation after the decimal point may be omitted.

[0014] The unsaturated group-containing alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention will be described below.

[0015] The photosensitive resin composition of the present invention contains an unsaturated group-containing alkali-soluble resin (A). Any resin can be used without particular limitation as long as it has an acid value sufficient to impart alkali developability and can be combined with the photopolymerizable monomer (B) to provide appropriate photocurability.

[0016] Examples of the alkali-soluble resin (A) having a carboxy group and a polymerizable unsaturated group in one molecule of the present invention include an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule, represented by general formula (3), which is obtained by reacting a reaction product of an epoxy compound (a-1) having two epoxy groups in one molecule, represented by general formula (6), and an unsaturated group-containing monocarboxylic acid with a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof (b), and a tetracarboxylic acid or an acid dianhydride thereof (c).

[0017] [ka]

[0018] (In formula (3), R1, R2, R3, and R4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; R5 is a hydrogen atom or a methyl group; A is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; Y is a tetravalent carboxylic acid residue; and Z is each independently a hydrogen atom or a substituent represented by general formula (4), with the proviso that at least one of Z is a substituent represented by general formula (4), and n is an integer of 1 to 20.)

[0019] [ka]

[0020] (In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0021] A method for producing an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by general formula (3) (hereinafter simply referred to as "alkali-soluble resin represented by general formula (3)") will be described in detail.

[0022] First, an epoxy compound (a-1) having two epoxy groups in one molecule and represented by general formula (6) (hereinafter, simply referred to as "epoxy compound (a-1) represented by general formula (6)") is reacted with an unsaturated group-containing monocarboxylic acid (e.g., (meth)acrylic acid) to obtain a diol compound containing a polymerizable unsaturated group.

[0023] [ka]

[0024] (In formula (6), R1, R2, R3, and R4 each 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-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond.)

[0025] The epoxy compound (a-1) is an epoxy compound having two glycidyl ether groups obtained by reacting a bisphenol with epichlorohydrin.

[0026] Examples of bisphenols used as raw materials for the epoxy compound (a-1) include bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl) ketone, 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) hexafluoropropane, and bis(4-hydroxy-3,5-dimethylphenyl) hexafluoropropane. propane, 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) 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-hydroxyphenyl)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'-biphenol, and the like.These may be used alone or in combination of two or more.

[0027] Examples of the unsaturated group-containing monocarboxylic acid compound include, in addition to acrylic acid and methacrylic acid, compounds obtained by reacting acrylic acid or methacrylic acid with an acid monoanhydride such as succinic anhydride, maleic anhydride, or phthalic anhydride.

[0028] The reaction between the epoxy compound (a-1) and (meth)acrylic acid can be carried out by a known method. For example, Japanese Patent Application Laid-Open No. 4-355450 describes that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 moles of (meth)acrylic acid per mole of an epoxy compound having two epoxy groups. In the present invention, the compound obtained by the above reaction is a diol compound containing a polymerizable unsaturated group, and is a diol (d) containing a polymerizable unsaturated group represented by general formula (7) (hereinafter, also simply referred to as "diol (d) represented by general formula (7)").

[0029] [ka]

[0030] (In formula (7), R1, R2, R3, and R4 each 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-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond.)

[0031] In the production of the alkali-soluble resin represented by general formula (3) by synthesis of the diol (d) represented by general formula (7), the subsequent addition reaction of a polyvalent carboxylic acid or its anhydride, and further reaction with a monofunctional epoxy compound having a polymerizable unsaturated group reactive with a carboxy group, the reaction is usually carried out in a solvent using a catalyst as necessary.

[0032] Examples of the solvent include cellosolve-based solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high-boiling ether or ester-based solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. There are no particular limitations on the reaction conditions such as the solvent and catalyst used, but it is preferable to use, for example, a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as the reaction solvent.

[0033] In addition, it is preferable to use a catalyst in the reaction between a carboxy group and an epoxy group. JP-A-9-325494 describes ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0034] Next, the diol (d) represented by general formula (7) obtained by the reaction of the epoxy compound (a-1) with (meth)acrylic acid is reacted with a tetracarboxylic acid or its dianhydride (b), and a dicarboxylic acid or tricarboxylic acid or its anhydride (c) to obtain an alkali-soluble resin having a carboxy group and a polymerizable unsaturated group in one molecule represented by general formula (3).

[0035] [ka]

[0036] (In formula (3), R1, R2, R3, and R4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group; R5 is a hydrogen atom or a methyl group; A is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, a fluorene-9,9-diyl group, or a direct bond; Y is a tetravalent carboxylic acid residue; and Z is each independently a hydrogen atom or a substituent represented by general formula (4), with the proviso that at least one of Z is a substituent represented by general formula (4), and n is an integer of 1 to 20.)

[0037] [ka]

[0038] (In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0039] The acid component used to synthesize the alkali-soluble resin represented by general formula (3) is a polyvalent acid component capable of reacting with the hydroxyl group in the diol (d) molecule represented by general formula (7), and it is necessary to use a dicarboxylic acid or tricarboxylic acid or an acid monoanhydride thereof (b) in combination with a tetracarboxylic acid or an acid dianhydride thereof (c). The carboxylic acid residue of the acid component may be either a saturated or unsaturated hydrocarbon group. In addition, these carboxylic acid residues may contain bonds containing heteroatoms such as -O-, -S-, and carbonyl groups.

[0040] As the dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b), chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their monoanhydrides, etc. can be used.

[0041] Examples of monoanhydrides of chain hydrocarbon dicarboxylic acids or tricarboxylic acids include monoanhydrides of succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and monoanhydrides of dicarboxylic acids or tricarboxylic acids having any substituent introduced therein. Examples of monoanhydrides of alicyclic dicarboxylic acids or tricarboxylic acids include monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like, and monoanhydrides of dicarboxylic acids or tricarboxylic acids having any substituent introduced therein. Examples of monoanhydrides of aromatic dicarboxylic acids or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like, and monoanhydrides of dicarboxylic acids or tricarboxylic acids having any substituent introduced therein.

[0042] Among the dicarboxylic acid or tricarboxylic acid monoanhydrides, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred.In addition, it is preferred to use the dicarboxylic acid or tricarboxylic acid monoanhydrides thereof.The above-mentioned dicarboxylic acid or tricarboxylic acid monoanhydrides may be used alone or in combination of two or more kinds.

[0043] As the tetracarboxylic acid or its dianhydride (c), a chain hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or their dianhydrides can be used.

[0044] Examples of the chain hydrocarbon tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and chain hydrocarbon tetracarboxylic acid having a substituent such as an alicyclic hydrocarbon group or an unsaturated hydrocarbon group introduced therein. Examples of the alicyclic tetracarboxylic acid include cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, and alicyclic tetracarboxylic acid having a substituent such as an chain hydrocarbon group or an unsaturated hydrocarbon group introduced therein. Examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone tetracarboxylic acid, and the like.

[0045] Among the tetracarboxylic acids or their dianhydrides, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, and diphenylethertetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenylethertetracarboxylic acid are more preferred. In addition, among the tetracarboxylic acids or their dianhydrides, it is preferred to use the dianhydrides. The above-mentioned tetracarboxylic acids or their dianhydrides may be used alone or in combination of two or more.

[0046] The reaction of the diol (d) represented by the general formula (7) with the acid components (b) and (c) is not particularly limited, and any known method can be used. For example, JP-A-9-325494 describes a method of reacting an epoxy (meth)acrylate with a tetracarboxylic dianhydride at a reaction temperature of 90 to 140°C.

[0047] Here, it is preferable to react the compound so that the terminals of the compound become carboxy groups, in such a manner that the molar ratio of the diol (d) represented by the general formula (7), the dicarboxylic acid or tricarboxylic acid or anhydride thereof (b), and the tetracarboxylic acid dianhydride (c) is (d):(b):(c)=1:0.01-1.0:0.2-1.0.

[0048] For example, when (b) acid monoanhydride and (c) acid dianhydride are used, it is preferable to react them so that the molar ratio [(d) / [(b) / 2+(c)]] of the amount of acid component to diol (d) represented by general formula (7) is 0.5 to 1.0. Here, when the molar ratio is 1.0 or less, the content of the diol compound containing unreacted polymerizable unsaturated groups is not increased, so the stability over time of the alkali-soluble resin composition can be improved. On the other hand, when the molar ratio exceeds 0.5, the terminal of the alkali-soluble resin represented by general formula (3) does not become an acid anhydride, so that the content of unreacted acid dianhydride can be suppressed from increasing, so the stability over time of the alkali-soluble resin composition can be improved. In addition, in order to adjust the acid value and molecular weight of the alkali-soluble resin represented by general formula (3), the molar ratio of each component (d), (b) and (c) can be arbitrarily changed within the above-mentioned range.

[0049] The acid value of the alkali-soluble resin represented by the general formula (3) is preferably in the range of 20 to 180 mgKOH / g, and more preferably 80 mgKOH / g or more and 120 mgKOH / g or less. When the acid value is 20 mgKOH / g or more, residues are less likely to remain during alkaline development, and when the acid value is 180 mgKOH / g or less, the penetration of the alkaline developer is not too fast, so peeling development can be suppressed. The acid value can be determined by titration with a 1 / 10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0050] The weight average molecular weight (Mw) of the alkali-soluble resin represented by the general formula (3) in terms of polystyrene as measured by gel permeation chromatography (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) is usually 1000 to 100000, preferably 2000 to 20000, and more preferably 2000 to 6000. When the weight average molecular weight is 1000 or more, it is possible to suppress a decrease in the adhesion of the pattern during alkali development. In addition, when the weight average molecular weight is less than 100000, it is easy to adjust the solution viscosity of the photosensitive resin composition to a suitable level for application, and alkali development does not take too long.

[0051] The content of component (A) in the photosensitive resin composition of the present invention is preferably 30 to 80 mass % based on the total mass of the solids when no colorant is contained, and is preferably 2 mass % or more and 70 mass % or less when a colorant is contained.

[0052] The photosensitive resin composition of the present invention contains (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds. The (B) component increases the adhesion of the cured film and also increases the solubility of the exposed area in an alkaline developer, thereby increasing the linearity reproducibility of the cured film. However, in order to prevent the cured film from becoming brittle, suppress a decrease in the acid value of the composition, increase the solubility of the unexposed area in an alkaline developer, and increase the linearity reproducibility of the cured film, it is preferable that the amount of the (B) component is not too high.

[0053] Examples of the photopolymerizable monomer (B) having at least two ethylenically unsaturated bonds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like. (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, and compounds having an ethylenic double bond, such as dendritic polymers having a (meth)acrylic group, may be used alone or in combination of two or more.

[0054] Examples of dendritic polymers having a (meth)acryloyl group as the compound having an ethylenic double bond include dendritic polymers obtained by adding a polyvalent mercapto compound to a part of the carbon-carbon double bonds in the (meth)acryloyl group of a polyfunctional (meth)acrylate. Specifically, there is a dendritic polymer obtained by reacting a (meth)acryloyl group of a polyfunctional (meth)acrylate represented by general formula (8) with a thiol group of a polyvalent mercapto compound represented by general formula (9).

[0055] [ka]

[0056] (In formula (8), R9 is a hydrogen atom or a methyl group, and R10 is R 11 (OH) k The remaining portion is obtained by donating l hydroxyl groups out of k hydroxyl groups to the ester bond in the formula. 11 (OH) k is a polyhydric alcohol based on a non-aromatic straight-chain or branched-chain hydrocarbon skeleton having 2 to 8 carbon atoms, a polyhydric alcohol ether formed by linking a plurality of molecules of the polyhydric alcohol via ether bonds by dehydration condensation of the alcohol, or an ester of such a polyhydric alcohol or polyhydric alcohol ether with a hydroxy acid. k and l are independently integers of 2 to 20, and k≧l.

[0057] [ka]

[0058] (In formula (9), R 12 is a single bond or a divalent to hexavalent C1 to C6 hydrocarbon group, and p is R 12 is a single bond, R 12 When is a divalent to hexavalent group, it is an integer of 2 to 6.

[0059] Examples of the polyfunctional (meth)acrylate represented by the general formula (8) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, and propylene oxide modified trimethylolpropane tri(meth)acrylate. , trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified Pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, epichlorohydrin-modified hexahydrophthalic acid di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified trimethylolpropane Examples of (meth)acrylic acid esters include trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimethylolpropane benzoate (meth)acrylate, tris((meth)acryloxyethyl)isocyanurate, alkoxy modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. These compounds may be used alone or in combination of two or more.

[0060] Examples of polyvalent mercapto compounds represented by general formula (9) include 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,4-dimercaptobutane, bisdimercaptoethanethiol, trimethylolpropane tri(mercaptoacetate), trimethylolpropane tri(mercaptopropionate), pentaerythritol tetra(mercaptoacetate), pentaerythritol tri(mercaptoacetate), pentaerythritol tetra(mercaptopropionate), dipentaerythritol hexa(mercaptoacetate), dipentaerythritol hexa(mercaptopropionate), etc. These compounds may be used alone or in combination of two or more.

[0061] In addition, when synthesizing the dendritic polymer, a polymerization inhibitor may be added as necessary. Examples of the polymerization inhibitor include hydroquinone compounds and phenol compounds. Specific examples of these include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, dibutylhydroxytoluene, and 2,4,6-tri-tert-butylphenol (BHT).

[0062] The blending ratio of the (A) component to the (B) component is preferably 30 / 70 to 90 / 10, more preferably 60 / 40 to 80 / 20, in terms of the weight ratio (A) / (B). When the blending ratio of the (A) component is 30 / 70 or more, the cured film after photocuring is less likely to become brittle, and the acid value of the coating film is less likely to become low in the unexposed areas, so that the decrease in solubility in an alkaline developer can be suppressed. Therefore, problems such as jagged pattern edges and lack of sharpness are less likely to occur. In addition, when the blending ratio of the (A) component is 90 / 10 or less, the ratio of photoreactive functional groups in the resin is sufficient, so that the desired crosslinked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility in an alkaline developer in the exposed areas is less likely to become high, so that the formed pattern can be prevented from becoming thinner than the target line width and from being missing.

[0063] The photosensitive resin composition of the present invention contains (C) an epoxy compound having a 3,4-epoxycyclohexyl group. Examples of (C) an epoxy compound having a 3,4-epoxycyclohexyl group include epoxy compounds represented by general formula (1) or general formula (2).

[0064] [ka]

[0065] (In formula (1), X is a single bond or a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom inside.)

[0066] [ka]

[0067] (In formula (2), a, b, c, and d each independently represent 0 or 1, and a+b+c+d=1 to 3.)

[0068] Here, X in the epoxy compound represented by general formula (1) is a single bond or a divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside. Examples of the divalent organic group having 1 to 20 carbon atoms which may contain a hetero element inside include a divalent hydrocarbon group, a divalent group having a carboxy group at one or two ends of the hydrocarbon group, etc. The above-mentioned hydrocarbon group may have an ether-bonded oxygen atom or an ester bond inside.

[0069] Examples of the divalent hydrocarbon group include straight-chain hydrocarbon groups such as methylene, ethylene, propylene, isopropylidene, sec-butylene, methylisobutylene, hexylene, decylene, and dodecylene. Examples of the divalent group having a carboxy group at the end of the hydrocarbon group include divalent organic groups represented by the general formulas (10) to (13). It is preferred that g is 1 in the general formula (10), h is 5 and i is 1 in the general formula (11), j is 2 in the general formula (12), and k is 4 and l is 1 in the general formula (13).

[0070] [ka]

[0071] (In formula (10), g is an integer of 1 to 20.)

[0072] [ka]

[0073] (In formula (11), h is an integer from 2 to 20, and i is an integer from 0 to 10.)

[0074] [ka]

[0075] (In formula (12), j is an integer of 1 to 20.)

[0076] [ka]

[0077] (In formula (13), k is an integer of 0 to 18, and l is an integer of 1 to 10.)

[0078] Examples of the epoxy compound represented by general formula (1) include the epoxy compounds represented by general formulas (14) to (20). Two or more of these epoxy compounds may be used in combination. Among the epoxy compounds represented by general formulas (14) to (20), the epoxy compounds represented by general formula (17) or (18), in which g is 1, h is 5, and i is 1, are preferred in terms of availability and the physical properties of the cured film.

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] (In formula (17), g is an integer of 1 to 20.)

[0084] [ka]

[0085] (In formula (18), h is an integer from 2 to 20, and i is an integer from 0 to 10.)

[0086] [ka]

[0087] (In formula (19), j is an integer of 1 to 20.)

[0088] [ka]

[0089] (In formula (20), k is an integer of 0 to 18, and l is an integer of 1 to 10.)

[0090] The content of the epoxy compound in component (C) is preferably 5 to 17% by mass based on the total mass of the solid content. By making the content of the epoxy compound in component (C) 5% by mass or more, it is possible to provide solvent resistance, and by making the content of the epoxy compound in component (C) 17% by mass or less, it is possible to provide solvent resistance and also to ensure sufficient adhesion of the pattern to the substrate.

[0091] Among the components (C), the epoxy compound represented by the general formula (2) is preferred. By using the epoxy compound represented by the general formula (2) having four epoxycyclohexyl groups in the molecule, the solvent resistance of the cured film (coating film) can be improved without using a curing agent or a curing accelerator.

[0092] The epoxy equivalent of the epoxy compound of component (C) is preferably 100 to 300 g / eq. The number average molecular weight (Mn) of the epoxy compound of component (C) is preferably 100 to 5000. When the epoxy equivalent is 100 to 300 g / eq and the number average molecular weight (Mn) of the epoxy compound is 100 to 5000, the development adhesion during development is ensured and a cured film with good solvent resistance can be obtained. When the epoxy equivalent is 300 g / eq or less, it is possible to design a photosensitive resin composition with an appropriate range of development speed, and the solvent resistance of the cured film can be ensured. It is more preferable to use an epoxy compound having three or more epoxy groups in one molecule. These compounds may be used alone or in combination of two or more.

[0093] The photosensitive resin composition of the present invention contains (D) a photopolymerization initiator.

[0094] Examples of the component (D) include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p'-bisdimethylaminobenzophenone; benzoins such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Biimidazole compounds such as 2-(o-chlorophenyl)-4,5-phenylbiimidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole, and 2,4,5-triarylbiimidazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)- Halomethyldiazole compounds such as 1,3,4-oxadiazole and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole; 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl) -Halomethyl-s-triazine compounds such as 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine;O-Acyloxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1-(4-phenylsulfanylphenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(4-methylsulfanylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylsulfanylphenyl)butan-1-one oxime-O-acetate; benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2 sulfur compounds such as 1-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and pentaerythritol tetrakis(3-mercaptopropionate); and tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone or in combination of two or more kinds.

[0095] In particular, when preparing a photosensitive resin composition containing a colorant, it is preferable to use O-acyloxime compounds (including ketoxime). Specific examples of the compound group include O-acyloxime photopolymerization initiators represented by general formula (5) or general formula (21). Among these compound groups, when using a colorant at a high pigment concentration or forming a light-shielding film pattern, it is preferable to use an O-acyloxime photopolymerization initiator having a molar absorption coefficient at 365 nm of 10,000 L / mol cm or more. In the present invention, the term "photopolymerization initiator" is used to include a sensitizer.

[0096] [ka]

[0097] (In formula (5), R6 and R7 are each independently a C1-C15 alkyl group, a C6-C18 aryl group, a C7-C20 arylalkyl group, or a C4-C12 heterocyclic group, and R8 is a C1-C15 alkyl group, a C6-C18 aryl group, or a C7-C20 arylalkyl group. Here, the alkyl group and the aryl group may be substituted with a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 alkanoyl group, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. In addition, the alkyl group may be any of linear, branched, and cyclic alkyl groups.)

[0098] [ka]

[0099] (In formula (21), R 13 and R 14 R are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a cycloalkylalkyl group, or an alkylcycloalkyl group having 4 to 10 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms. 15 are each independently a linear or branched alkyl or alkenyl group having 2 to 10 carbon atoms, and some of the -CH2- groups in the alkyl or alkenyl group may be substituted with -O- groups. 13 ~R 15 A part of the hydrogen atoms in the group may be substituted with halogen atoms.

[0100] The content of component (D) is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total mass of components (A) and (B). When the content of component (D) is 0.1% by mass or more, the photopolymerization speed is adequate, and a decrease in sensitivity can be suppressed. When the content of component (D) is 30% by mass or less, the line width can be faithfully reproduced on the mask, and the pattern edge can be sharpened.

[0101] The photosensitive resin composition of the present invention contains a solvent (E).

[0102] Examples of the solvent contained in the (E) photosensitive resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy-2-butanone, and diacetone alcohol; terpenes such as α- or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diethylene glycol ethyl methyl ether, and propylene glycol. Examples of the solvent include glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; and esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing using these, a homogeneous solution-like composition can be obtained. These solvents may be used alone or in combination of two or more to obtain the required characteristics such as coatability.

[0103] The content of the component (E) varies depending on the target viscosity, but is preferably 60 to 90% by mass in the photosensitive resin composition solution.

[0104] The photosensitive resin composition of the present invention may contain (F) a curing agent and / or a curing accelerator for the epoxy compound. When the photosensitive resin composition of the present invention is a composition that is baked at a low temperature of 140° C. or less, the curing of the component (C) is likely to be insufficient, so the photosensitive resin composition preferably contains the component (F) in order to sufficiently cure the component (C).

[0105] Examples of the curing agent for the epoxy compound, which is the component (F), include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, Lewis acid complex compounds, etc. In the present invention, polycarboxylic acid compounds can be preferably used.

[0106] Examples of polycarboxylic acid compounds include polycarboxylic acids, polycarboxylic anhydrides, and polycarboxylic heat decomposable esters. Polycarboxylic acids refer to compounds having two or more carboxy groups in one molecule, such as succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-4,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,4-tricarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, etc. Examples of polycarboxylic acid anhydrides include the acid anhydrides of the above compounds. These may be intermolecular acid anhydrides, but generally, acid anhydrides that are ring-closed within a molecule are used. Examples of the thermally decomposable esters of polycarboxylic acids include t-butyl esters, 1-(alkyloxy)ethyl esters, and 1-(alkylsulfanyl)ethyl esters of the above compounds (wherein alkyl is a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have a branched or cyclic structure and may be substituted with any substituent). In addition, polymers or copolymers having two or more carboxy groups can also be used as the polycarboxylic acid compound, and the carboxy groups may be anhydrides or thermally decomposable esters.

[0107] Examples of the polymer or copolymer include a polymer or copolymer containing (meth)acrylic acid as a constituent, a copolymer containing maleic anhydride as a constituent, and a compound obtained by reacting a tetracarboxylic dianhydride with a diamine or diol to open the ring of the acid anhydride. Of these, it is preferable to use anhydrides of phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and benzene-1,2,4-tricarboxylic acid. When a polycarboxylic acid compound is used as a curing agent for an epoxy compound, the blending ratio is preferably such that the carboxyl group of the polycarboxylic acid compound is 0.5 to 1.0 mol, more preferably 0.6 to 0.95 mol, per 1 mol of the epoxy group of the epoxy compound.

[0108] As the curing accelerator for the epoxy compound, which is the component (F), known compounds known as curing accelerators for epoxy compounds, curing catalysts, latent curing agents, etc. can be used. Examples of the curing accelerator for the epoxy compound include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc. Among the above curing accelerators, 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene or salts thereof are preferred.

[0109] The amount of the curing accelerator added is preferably 0.05 to 2 parts by mass based on 100 parts by mass of the epoxy compound, and the amount can be adjusted depending on the state of chemical resistance of the resin film pattern after thermal curing.

[0110] The total amount of the components (C) and (F) is preferably 6 to 24% by mass, and more preferably 8 to 22% by mass, based on the total mass of the solids. By including sufficient amounts of the components (C) and (F), the line width reproducibility, linearity reproducibility, and solvent resistance of the formed cured film can be sufficiently improved.

[0111] Also, the equivalent number E of the epoxy group of component (C) epThe ratio of the equivalent number of the epoxy compound curing agent in component (F) to the equivalent number of the epoxy compound curing agent in component (F) is E ep It is preferable that E / hardening agent=1.5 to 2.5. ep When the curing agent ratio is 1.5 or more, the epoxy compound can be sufficiently cured, so that it is possible to suppress the unreacted epoxy compound from remaining in the photosensitive resin composition. ep When the curing agent ratio is 2.5 or less, the adhesion and linearity reproducibility of the cured film can be sufficiently improved.

[0112] The photosensitive resin composition of the present invention may contain a colorant (G).

[0113] The colorant is preferably a colorant selected from the group consisting of organic pigments or inorganic pigments, and more preferably a light-shielding material selected from the group consisting of organic black pigments or inorganic black pigments. The content of the colorant, which is the component (G), can be arbitrarily determined according to the desired light-shielding degree, but is preferably 20 to 80 mass% relative to the solid components in the photosensitive resin composition, and more preferably 40 to 70 mass%. When the colorant is 20 mass% or more relative to the solid components in the photosensitive resin composition, sufficient light-shielding properties can be obtained. When the colorant is 80 mass% or less relative to the solid components in the photosensitive resin composition, the content of the photosensitive resin, which is the original binder, does not decrease, and desired development characteristics and film-forming ability can be obtained.

[0114] Examples of black organic pigments as the component (G) include perylene black, aniline black, cyanine black, and lactam black. Examples of mixed-color organic pigments include those in which at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments are mixed together to produce a pseudo-black color. Examples of black inorganic pigments include carbon black, chromium oxide, iron oxide, and titanium black. These (G) components may be used alone or in combination of two or more types depending on the function of the intended photosensitive resin composition. Among the above pigments, carbon black is preferred from the viewpoints of light-shielding properties, surface smoothness, dispersion stability, and affinity with resins. In addition, when using organic pigments, they should be finely processed to achieve fine dispersion with an average particle size of 50 nm or less (specific surface area according to the BET method of 50 m2 or less). 2 / g or more) is preferred.

[0115] Examples of organic pigments that can be used as component (G) include, but are not limited to, those having the following Color Index numbers: Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279 etc. Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81 etc. Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214 etc. Pigment Green 7, 36, 58 etc. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80 etc. Pigment Violet 19, 23, 37 etc.

[0116] In addition, it is preferable that the colorant (G) component is dispersed in advance in a solvent together with a dispersant to form a colorant dispersion liquid, and then blended as a photosensitive resin composition for colored film. Here, the solvent for dispersion can be any of those mentioned above. Among the above-mentioned solvents, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. are preferred.

[0117] The dispersant may be any known dispersant such as various polymer dispersants. Examples of the dispersant include known compounds (compounds commercially available under the names of dispersant, dispersing wetting agent, dispersion promoter, etc.) that have been conventionally used for pigment dispersion and may be used without any particular limitation. Examples of the dispersant include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative dispersants (dispersion assistants), etc. In particular, it is preferable to use a cationic polymer dispersant having 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 the pigment, an amine value of 1 to 100 mgKOH / g, and a number average molecular weight of 1,000 to 100,000. The blending amount of the dispersant is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, based on the colorant.

[0118] In addition, when preparing the colorant dispersion, a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A) may be co-dispersed in addition to the dispersant. By co-dispersing a part of the polymerizable unsaturated group-containing alkali-soluble resin of the component (A), it is possible to obtain a photosensitive resin composition that is easy to maintain high exposure sensitivity, has good adhesion during development, and is less likely to cause residue problems. In this case, the amount of the component (A) in the colorant dispersion is preferably 2 to 20 mass %, more preferably 5 to 15 mass %. When the component (A) is 2 mass % or more, effects such as improved sensitivity, improved adhesion, and reduced residue due to co-dispersion can be obtained. When the component (A) is 20 mass % or less, even when the content of the colorant is particularly large, the viscosity of the colorant dispersion does not become too high and the colorant can be uniformly dispersed. The obtained colorant dispersion is mixed with the components (A) to (F) and, if necessary, other components are added to adjust the viscosity to a level suitable for the film formation conditions, thereby making it possible to obtain a photosensitive resin composition used in the production method of the present invention.

[0119] The photosensitive resin composition of the present invention preferably contains (H) silica particles.

[0120] The silica particles, which are component (H), are not particularly limited in terms of the manufacturing method (such as gas phase reaction or liquid phase reaction) or the shape (spherical, non-spherical). In addition, silica particles that have been surface-treated with a silane coupling agent or the like can also be used without any particular limitations.

[0121] The type of silica particles, which is the component (H) used in the present invention, is not particularly limited. Solid silica may be used, or hollow silica particles may be used. Note that "hollow silica particles" refer to silica particles that have a cavity inside the particle.

[0122] By using the silica particles, the refractive index of the light-shielding film containing the silica particles can be reduced.

[0123] The average particle size of the silica particles is preferably 1 to 95 nm, and more preferably 5 to 90 nm. By using silica particles with a small average particle size, it is possible to suppress wobbling of the side surface of the fine line pattern. In addition, there is an effect of reducing unevenness on the surface of the cured film (coating film), and it is possible to suppress variations in reflectance within the surface of the cured film (coating film).

[0124] The content of the silica particles is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, based on the total mass of the photosensitive resin composition. When the content of the silica particles is within the above range, a low reflectance can be achieved while good patterning properties can be ensured.

[0125] The average particle size of the silica particles can be measured by the cumulant method using a dynamic light scattering particle size distribution analyzer "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.).

[0126] The refractive index of the silica particles can be 1.10 to 1.47. In addition to being able to use ordinary silica particles with a refractive index of 1.45 to 1.47, the refractive index of the light-shielding film can be made lower than that of a light-shielding film containing only ordinary silica particles by using hollow silica particles having a low refractive index.

[0127] The refractive index of the silica particles can be determined from a transparent mixture obtained by mixing the silica particles powdered with a standard refractive index liquid having a known refractive index. In this case, the refractive index of the standard refractive index liquid of the mixture is taken as the refractive index of the silica particles. The refractive index of the silica particles can be measured using an Abbe refractometer.

[0128] Furthermore, since reflection caused by the difference in refractive index between the layer formed on the cured film (coating film) and the cured film (coating film) to be formed can be suppressed, reflection can be suppressed without the need to provide a separate anti-reflection film or the like.

[0129] The silica particles may have a spherical or elliptical shape, but the silica particles used in the present invention are preferably spherical.

[0130] The silica particles preferably have a sphericity of 1.0 to 1.5. If the sphericity of the silica particles is within this range, the particle shape is close to a perfect sphere. Therefore, the silica particles can be uniformly filled in a thin light-shielding film, and the light-shielding film can be formed in which the silica particles are not exposed to the outside from the film surface while maintaining the film surface smoothness. Therefore, a light-shielding film having a low refractive index and sufficient strength can be obtained. When trying to obtain a light-shielding film that can realize low reflection on the film surface side, the selection of a photopolymerization initiator is also an important factor, and it is preferable to use an oxime ester-based photopolymerization initiator that is generally used in light-shielding films and add a thiol compound in an amount of 0.5 to 5% in the solid content.

[0131] The sphericity of the silica particles can be determined from the ratio of the longest diameter to the shortest diameter (average value of 100 arbitrary silica particles). Here, the longest diameter and the shortest diameter of the silica particles are values ​​determined by photographing the silica particles with a transmission electron microscope and measuring the longest diameter and the shortest diameter of the silica particles from the obtained micrograph.

[0132] The silica particles, which are the component (H), can be dispersed in a solvent to form a silica particle dispersion, which can be mixed with other formulation components. The dispersant can be any known compound (compounds commercially available under the names of dispersant, dispersing wetting agent, dispersion promoter, etc.) used for dispersing pigments (light-shielding components) without any particular restrictions.

[0133] The photosensitive resin composition of the present invention may contain additives such as a thermal polymerization inhibitor, an antioxidant, a plasticizer, a filler, a leveling agent, an antifoaming agent, a surfactant, and a coupling agent, if necessary. Examples of the thermal polymerization inhibitor and the antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and a hindered phenol compound. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and the leveling agent include silicone-based, fluorine-based, and acrylic-based compounds. Examples of the surfactant include fluorine-based surfactants and silicone-based surfactants. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

[0134] The method for producing a cured film of the present invention comprises applying the above-described photosensitive resin composition onto a substrate having a heat resistance temperature of 140°C or less, exposing the substrate to light through a photomask, removing the unexposed areas by development, and heating the substrate at a temperature of 140°C or less to form a predetermined cured film pattern.

[0135] Examples of substrates used in the method for producing a cured film of the present invention include resin films (plastic substrates) such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) having a heat-resistant temperature of 140° C. or less, and substrates on which electrodes such as ITO and gold are vapor-deposited or patterned on a resin film. Here, the term "heat-resistant temperature" refers to a temperature at which problems such as deformation do not occur even if the substrate is exposed during a processing process such as pattern formation of a cured film on the substrate. Note that the temperature of the resin film changes depending on the degree of stretching treatment, but it is necessary that the temperature does not exceed at least the glass transition temperature (Tg).

[0136] Examples of other substrates used in the method for producing a cured film of the present invention include those having a high heat resistance of the substrate itself, such as a glass substrate, a silicon wafer, and a polyimide film, but on which a thin film having low heat resistance is formed. Specific examples of other substrates include substrates with organic devices, such as glass, a silicon wafer, or a polyimide film, on which an organic electroluminescence (OLED) or an organic thin film transistor (TFT) is formed. The heat-resistant temperature of the substrate having low heat resistance targeted in the present invention varies depending on the type of resin and the device, but is preferably 80 to 140°C. The substrate with an organic device also includes those on which a protective film, a protective film, etc. is formed after the formation of the organic device. This is because even if the heat resistance of these protective films and protective films themselves is 150°C or higher, if the heat resistance is substantially only 140°C or lower in order to ensure the function of the organic device, they are considered to be substrates with organic devices.

[0137] The photosensitive resin composition of the present invention can be applied to a substrate by any method, including known solution immersion and spraying methods, as well as methods using a roller coater, land coater, slit coater, or spinner. After application to a desired thickness by these methods, the solvent is removed (prebaked) to form a coating. Prebaking is performed by heating in an oven, a hot plate, or the like. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 60 to 110° C. (set so as not to exceed the heat resistance temperature of the substrate) for 1 to 3 minutes.

[0138] The exposure performed after the pre-baking is performed by an ultraviolet exposure device, and only the resist in the portion corresponding to the pattern is exposed by exposing through a photomask. The exposure device and its exposure irradiation conditions are appropriately selected, and the 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. Preferably, the photocure is performed by irradiating a certain amount of light with a wavelength of 365 nm.

[0139] Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays, and the wavelength range of the radiation is preferably 250 to 450 nm. Examples of developers suitable for this alkaline development include aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, and tetramethylammonium hydroxide. These developers can be appropriately selected according to the characteristics of the resin layer, and surfactants may be added as necessary. The development temperature is preferably 20 to 35°C, and fine images can be precisely formed using a commercially available developing machine or ultrasonic cleaner. After alkaline development, the film is usually washed with water. Examples of development methods that can be used include shower development, spray development, dip (immersion) development, and puddle (liquid puddle) development.

[0140] Alkaline development after exposure is carried out for the purpose of removing the resist in the unexposed areas, and a desired pattern is formed by this development. Examples of developers suitable for this alkaline development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydroxides of alkali metals, etc. In particular, it is preferable to carry out development at a temperature of 23 to 28°C using a weakly alkaline aqueous solution containing 0.05 to 3.0 mass% of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate. In addition, fine images can be precisely formed using a commercially available developing machine, ultrasonic cleaner, etc.

[0141] After development, a heat treatment (post-baking) is preferably performed at a temperature of 80 to 140°C (set so as not to exceed the heat resistance temperature of the substrate) for 20 to 90 minutes, and more preferably at a temperature of 90 to 120°C for a heating time of 30 to 60 minutes. The post-baking is performed for the purpose of increasing the adhesion between the patterned cured film and the substrate, etc. This is performed by heating in an oven, a hot plate, etc., in the same manner as in the pre-baking. The patterned cured film of the present invention is formed through each step of the photolithography method described above. EXAMPLES

[0142] Hereinafter, the embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these.

[0143] First, synthesis examples of the alkali-soluble resin having a polymerizable unsaturated group represented by the general formula (3) will be described. The resins in these synthesis examples were evaluated as follows unless otherwise specified.

[0144] [Solid content concentration] 1 g of the resin solution obtained in Synthesis Example was impregnated into a glass filter (weight: W0(g)), weighed [W1(g)], and the weight after heating at 160°C for 2 hours [W2(g)] was calculated from the following formula. Solid content concentration (weight%) = 100 × (W2-W0) / (W1-W0)

[0145] [Epoxy equivalent] The resin solution was dissolved in dioxane, and then a solution of tetraethylammonium bromide in acetic acid was added. The content was determined by titration with a 1 / 10N perchloric acid solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0146] [Acid value] The resin solution was dissolved in dioxane and titrated with a 1 / 10N KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to determine the content.

[0147] [Molecular weight] Measurement was performed using gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, columns: TSKgelSuperH-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuperH-5000 (1 column) (manufactured by Tosoh Corporation), temperature: 40°C, rate: 0.6 ml / min), and the weight average molecular weight (Mw) was calculated as a value converted into standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0148] [Molar extinction coefficient] The molar absorption coefficient of the acyloxime-based photopolymerization initiator was measured using a UV-Vis-NIR spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0149] [Average particle size] The average particle size of the silica particles was measured by the cumulant method using a dynamic light scattering particle size distribution analyzer "Particle Size Analyzer FPAR-1000" (manufactured by Otsuka Electronics Co., Ltd.).

[0150] The abbreviations used in the Synthesis Examples and Comparative Examples are as follows. DCPMA: dicyclopentanyl methacrylate GMA: Glycidyl methacrylate St: styrene AA: Acrylic acid SA: Succinic anhydride BPFE: Bisphenol fluorene type epoxy compound (reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxirane) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride THPA: Tetrahydrophthalic anhydride AIBN: Azobisisobutyronitrile TDMAMP: Trisdimethylaminomethylphenol HQ: Hydroquinone TEA: Triethylamine TEAB: Tetraethylammonium bromide PGMEA: Propylene glycol monomethyl ether acetate

[0151] [Synthesis Example 1] PGMEA (300 g) was placed in a 1 L four-neck flask equipped with a reflux condenser, and the flask was purged with nitrogen and then heated to 120° C. A monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol) dissolved in AIBN (10 g) was added dropwise from a dropping funnel to the flask over 2 hours, and the mixture was stirred at 120° C. for another 2 hours to obtain a copolymer solution.

[0152] Next, after replacing the inside of the flask system with air, AA (24.0 g, 95% of glycidyl group), TDMAMP (0.8 g) and HQ (0.15 g) were added to the obtained copolymer solution and stirred at 120 ° C for 6 hours to obtain a polymerizable unsaturated group-containing copolymer solution. SA (30.0 g, 90% of the moles of AA added) and TEA (0.5 g) were added to the obtained polymerizable unsaturated group-containing copolymer solution and reacted at 120 ° C for 4 hours to obtain a polymerizable unsaturated group-containing alkali-soluble copolymer resin solution (A)-1. The solid content concentration of the resin solution was 46.0 mass%, the acid value (solid content equivalent) was 76 mg KOH / g, and the Mw by GPC analysis was 5300.

[0153] [Synthesis Example 2] BPFE (114.4g, 0.23mol), AA (33.2g, 0.46mol), PGMEA (157.0g) and TEAB (0.48g) were charged into a 500ml four-neck flask equipped with a reflux condenser, and the mixture was stirred at 100-105°C for 20 hours to react. Next, BPDA (35.3g, 0.12mol) and THPA (18.3g, 0.12mol) were charged into the flask, and the mixture was stirred at 120-125°C for 6 hours to obtain a polymerizable unsaturated group-containing alkali-soluble resin (A)-2. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (solid content equivalent) was 103mgKOH / g, and the Mw by GPC analysis was 3600.

[0154] The photosensitive resin compositions of Examples 1 to 43 and Comparative Examples 1 to 36 were prepared by mixing the above-mentioned components in the ratios shown in Tables 1 to 7. All values ​​in Tables 1 to 7 are in parts by mass. In Tables 1 to 7, the polymerizable unsaturated group-containing alkali-soluble resin is described as the resin.

[0155] (Polymerizable unsaturated group-containing alkali-soluble resin) (A)-1: Resin solution obtained in Synthesis Example 1 above (solid content concentration: 46.0% by mass) (A)-2: Resin solution obtained in Synthesis Example 2 above (solid content concentration: 56.1% by mass)

[0156] (Photopolymerizable monomer) (B): Mixture of dipentaerythritol pentaacrylate and hexaacrylate (DPHA (acrylic equivalent: 96-115), manufactured by Nippon Kayaku Co., Ltd.)

[0157] (Epoxy compounds) (C)-1: 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (epoxy equivalent: 130, manufactured by Daicel Corporation) (C)-2: butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone (epoxy equivalent 197, Daicel Corporation) (C)-3: HiREM-1 (epoxy equivalent: 113, manufactured by Shikoku Chemical Industry Co., Ltd.) (C)-4: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150, epoxy equivalent 180, manufactured by Daicel Corporation) (C)-5: Triphenylmethane type epoxy resin (EPPN-501H, epoxy equivalent 160, manufactured by Nippon Kayaku Co., Ltd.)

[0158] (Photopolymerization initiator) (D)-1: Oxime ester photopolymerization initiator (ADEKA ARCLES NCI-831, manufactured by ADEKA Corporation, "ADEKA ARCLES" is a registered trademark of the company) (D)-2: Pentaerythritol tetrakis(3-mercaptopropionate)

[0159] (solvent) (E)-1: Propylene glycol monomethyl ether acetate (PGMEA) (E)-2: Diethylene glycol ethyl methyl ether (EDM)

[0160] (Hardening agent and hardening accelerator) (F)-1: Trimellitic anhydride (F)-2: PGMEA solution containing 2.0% by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU®, manufactured by San-Apro Co., Ltd.)

[0161] (Coloring material) (G)-1: Pigment dispersion of 25.0% by mass of resin-coated carbon black and 5.0% by mass of polymer dispersant in PGMEA solvent (solid content concentration 30.0% by mass) (G)-2: Pigment dispersion (solid content concentration 35.0% by mass) of 25.0% by mass of carbon black, 2.0% by mass of polymer dispersant, and 8.0% by mass of dispersing resin (alkali-soluble resin (A)-2 of Synthesis Example 2) in PGMEA solvent

[0162] (H)-1: Silica PGMEA dispersion "YA010C" (manufactured by Admatechs Co., Ltd., solid content concentration 20 mass%, average particle size 10 nm) (H)-2: Silica PGMEA dispersion "YA050C" (manufactured by Admatechs Co., Ltd., solid content concentration 40 mass%, average particle size 50 nm) (H)-3: Silica PGMEA dispersion "YC100C" (manufactured by Admatechs Co., Ltd., solid content concentration 50 mass%, average particle size 100 nm) (H)-4: Hollow silica isopropanol dispersion (manufactured by JGC Catalysts and Chemicals Co., Ltd., solid content concentration 20 mass%, average particle size 75 nm, porosity 46 volume%)

[0163] (Surfactant) (I): Megafac F-475 (manufactured by DIC Corporation, "Megafac" is a registered trademark of the company)

[0164] [Table 1]

[0165] [Table 2]

[0166] [Table 3]

[0167] [Table 4]

[0168] [Table 5]

[0169] [Table 6]

[0170] [Table 7]

[0171] [evaluation] The following evaluations were carried out using the cured films (coating films) obtained by curing the photosensitive resin compositions of Examples 1 to 43 and Comparative Examples 1 to 36. The evaluation results are shown in Tables 8 to 13.

[0172] (Preparation of cured film (coating film) for evaluating development characteristics) The photosensitive resin compositions shown in Tables 1 to 7 were each subjected to irradiation with a low-pressure mercury lamp at a wavelength of 254 nm and an illumination intensity of 1000 mJ / cm 2 The coating was applied using a spin coater onto a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 1000 nm so that the film thickness after heat curing would be 1.2 μm, and the coating was prebaked using a hot plate at 85°C for 1 minute to produce a cured film (coating). Next, the exposure gap was adjusted to 100 μm, and a negative photomask with a line / space of 10 μm / 50 μm was placed on the cured film (coating), and the i-line illuminance was 30 mW / cm.2 80mJ / cm with ultra-high pressure mercury lamp 2 The exposed portion was exposed to ultraviolet light to cause a photocuring reaction.

[0173] Next, the exposed cured film (coating film) was soaked in a 0.04% potassium hydroxide solution at 25°C at 1 kgf / cm 2 After development for 10 and 20 seconds from the development time (break time = BT) when the pattern begins to appear, the shower pressure was increased to 5 kgf / cm 2 The unexposed portions of the cured film (coating film) were removed to form a cured film pattern on the glass substrate, which was then main-cured (post-baked) at 85°C for 60 minutes using a hot air dryer to obtain substrates with cured films according to Examples 1 to 43 and Comparative Examples 1 to 36.

[0174] [Development characteristic evaluation] (Pattern line width) (Evaluation method) The pattern line width after the main curing (post-baking) was measured with a length measuring microscope "XD-20" (Nikon Corporation) with a mask width of 10 μm. The pattern line width was evaluated in the cases of BT+10 seconds and BT+20 seconds.

[0175] (Evaluation Criteria) ○: Pattern line width is within the range of 10±2 μm ×: Pattern line width is outside the range of 10±2 μm

[0176] (Pattern linearity) (Evaluation method) The 10μm mask pattern after the main curing (post-baking) was observed using an optical microscope. The pattern linearity was evaluated in the cases of BT+10 seconds and BT+20 seconds. A score of △ or higher was considered to be acceptable.

[0177] (Evaluation Criteria) ○: No jagged edges are observed on the pattern edges. △: Jagged edges are observed in some areas of the pattern. ×: Jagged edges of the pattern are observed throughout the entire pattern.

[0178] (Pattern adhesion) (Evaluation method) The 10 μm mask pattern after main curing (post-baking) was observed using an optical microscope. The pattern adhesion was evaluated under development conditions of BT+20 seconds, and a score of △ or higher was considered to be acceptable.

[0179] (Evaluation Criteria) ○: No peeling is observed in the pattern △: Peeling is observed in a small part of the pattern. ×: Most of the pattern is peeled off

[0180] (Preparation of cured film (coating film) for optical density (OD) evaluation) The photosensitive resin compositions shown in Tables 1 to 7 were each subjected to irradiation with a low-pressure mercury lamp at a wavelength of 254 nm and an illumination intensity of 1000 mJ / cm 2 The coating was applied using a spin coater onto a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 1000 nm so that the film thickness after heat curing would be 1.2 μm, and the coating was prebaked using a hot plate at 85°C for 1 minute to produce a cured film (coating). Next, the exposure gap was adjusted to 100 μm, and a negative photomask with a line / space of 10 μm / 50 μm was placed on the cured film (coating), and the i-line illuminance was 30 mW / cm. 2 80mJ / cm with ultra-high pressure mercury lamp 2 The photocuring reaction was carried out by irradiating the film with ultraviolet light.

[0181] Next, the exposed cured film (coating film) was soaked in a 0.04% potassium hydroxide solution at 25°C at 1 kgf / cm 2 After development for 20 seconds from the development time (break time = BT) when the pattern begins to appear, the shower pressure was increased to 5 kgf / cm 2The unexposed portions of the cured film (coating film) were removed to form a cured film pattern on the glass substrate, and the cured film (coating film) was post-cured (post-baked) for 60 minutes at 85°C using a hot air dryer to obtain the cured films (coating films) of Examples 9 to 43 and Comparative Examples 9 to 36.

[0182] [Optical density evaluation] (Evaluation method) The optical density (OD) of the prepared cured film (coating film) was evaluated using a Macbeth transmission densitometer. In addition, the thickness of the cured film (coating film) formed on the substrate was measured, and the optical density (OD) value was divided by the film thickness to obtain OD / μm.

[0183] The optical density (OD) was calculated using the following formula (1). Optical density (OD)=-log 10 T(1) (T indicates transmittance)

[0184] [Solvent resistance evaluation] (Evaluation method) The surface of the cured film (coating film) prepared in the same manner as for the evaluation of optical density (OD) was rubbed back and forth 20 times with a cloth soaked in PGMEA.

[0185] (Evaluation Criteria) ○: No dissolution or damage was observed on the surface of the cured film (coating film). △: Dissolution is observed in a small area of ​​the surface of the cured film (coating film), and there are also small scratches. ×: The surface of the cured film (coating film) is softened and most of it is scratched.

[0186] (Preparation of cured film (coating film) for reflectance evaluation) The photosensitive resin compositions shown in Tables 1 to 7 were each subjected to irradiation with a low-pressure mercury lamp at a wavelength of 254 nm and an illumination intensity of 1000 mJ / cm 2The coating was applied using a spin coater onto a 125 mm x 125 mm glass substrate "#1737" (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") whose surface had been cleaned by irradiating it with ultraviolet light of 1000 W, so that the film thickness after heat curing would be 1.2 μm, and the coating was prebaked using a hot plate at 85°C for 1 minute to produce a cured film (coating film). Next, the coating was main cured (post-baked) for 60 minutes at 85°C using a hot air dryer to obtain substrates with cured films according to Examples 9 to 43 and Comparative Examples 9 to 36.

[0187] [Reflectance evaluation] (Evaluation method) The reflectance of the cured film (coating film) side of the substrate thus prepared with the cured film (coating film) was measured at an incident angle of 2° using an ultraviolet-visible-near infrared spectrophotometer "UH4150" (manufactured by Hitachi High-Tech Science Corporation).

[0188] [Table 8]

[0189] [Table 9]

[0190] [Table 10]

[0191] [Table 11]

[0192] [Table 12]

[0193] [Table 13]

[0194] From the evaluation results of Examples 25 to 32, it was found that sufficient light-shielding properties could be obtained and desired development characteristics (pattern line width, pattern linearity) could be obtained by setting the content of the coloring material, which is the component (G), to 20 to 80 mass% based on the solid content in the photosensitive resin composition. This is believed to be because the content of the photosensitive resin, which is the original binder, is sufficient to make the development characteristics, especially the pattern linearity, appropriate.

[0195] From the evaluation results of Examples 1 to 43 and Comparative Examples 1 to 36, it was found that when the mass of component (C) in the solid content is in the range of 5 to 17 mass%, a cured film (coating film) that satisfies the solvent resistance and has excellent pattern adhesion can be obtained. On the other hand, it was found that when the mass of component (C) is 4 mass% or less of the total solid content, the solvent resistance of the cured film (coating film) is insufficient, and when it exceeds 17 mass%, the solvent resistance of the cured film (coating film) is satisfactory, but the adhesion of the pattern is reduced and the pattern peeling during development becomes noticeable.

[0196] The results of Comparative Examples 33 to 36 show that by using an epoxy compound having an epoxycyclohexyl group as component (C), a cured film (coating film) having better solvent resistance can be obtained than in a system using an epoxy compound having a glycidyl group.

[0197] It was found that the cured films (coating films) of Examples 1 to 43, which contained (C)-1 to (C)-3 having epoxycyclohexyl groups as the (C) component, generally had excellent solvent resistance. In particular, it was found that the use of (C)-2 having four epoxycyclohexyl groups in the molecule as the (C) component was effective in improving the solvent resistance of the cured film (coating film).

[0198] The results of Examples 39 to 43 show that the reflectance measured from the coating surface can be reduced by adding (H) silica particles. In particular, it is believed that this is because the use of solid / hollow silica particles having a small average particle size of 1 to 95 nm can reduce the unevenness of the cured film (coating) surface, thereby suppressing the variation in reflectance within the cured film (coating) surface. [Industrial Applicability]

[0199] The photosensitive resin composition of the present invention can form a cured film pattern having a line width within the range of 10±2 μm, excellent development adhesion and linearity, and good solvent resistance, even if the process of forming the cured film pattern does not include a step of thermal curing at a temperature exceeding 140 ° C. For this reason, a cured film pattern having the above-mentioned characteristics can be formed on a resin film such as PET or PEN, which has a heat resistance temperature of 140 ° C. or less, and on a substrate with an organic device such as an organic EL or organic TFT on a glass substrate or a silicon wafer. The photosensitive resin composition of the present invention is suitable for providing a cured film such as a transparent film pattern, an insulating film pattern, a black matrix, a partition pattern, etc., which are necessary when forming a color filter, an organic EL pixel, or a touch panel, on a substrate with a low heat resistance temperature, and these substrates with cured films can be used for the manufacture of display devices such as liquid crystal and organic EL, and the manufacture of solid-state imaging elements such as CMOS, and touch panels.

Claims

1. (A) an unsaturated group-containing alkali-soluble resin; (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds; (C) an epoxy compound having two or more 3,4-epoxycyclohexyl groups; (D) a photopolymerization initiator; (E) a solvent; (F) a curing agent and / or a curing accelerator for the epoxy compound; The unsaturated group-containing alkali-soluble resin of the component (A) is an unsaturated group-containing alkali-soluble resin represented by general formula (3), 【Chemistry 1】 (In formula (3), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group; 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-, a fluorene-9,9-diyl group or a direct bond; Y is a tetravalent carboxylic acid residue; and Z is each independently a hydrogen atom or a substituent represented by general formula (4), with the proviso that one or more of Z's are a substituent represented by general formula (4), and n is an integer from 1 to 20.) 【Chemistry 2】 (In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.) The content of the component (C) is 5 to 17% by mass based on the total mass of the solid content, The component (F) contains a polycarboxylic acid compound, The blending ratio of the polycarboxylic acid compound is such that the amount of the carboxyl group of the polycarboxylic acid compound is 0.5 to 1.0 moles per mole of the epoxy group of the epoxy compound (C), The content of the colorant (G) selected from the group consisting of organic pigments and inorganic pigments is 0 mass% or more and 40 mass% or less based on the total mass of the solid content. Photosensitive resin composition.

2. 2. The photosensitive resin composition according to claim 1, wherein the component (C) is an epoxy compound represented by general formula (1) or general formula (2). 【Chemistry 3】 (In formula (1), X is a single bond or a divalent organic group having 1 to 20 carbon atoms which may contain a heteroatom therein.) 【Chemistry 4】 (In formula (2), a, b, c, and d each independently represent 0 or 1, and a+b+c+d=1 to 3.)

3. The photosensitive resin composition described in claim 1 or 2, wherein the (C) component is an epoxy compound represented by general formula (2). 【Chemistry 5】 (In formula (2), a, b, c, and d each independently represent 0 or 1, and a+b+c+d=1 to 3.)

4. The photosensitive resin composition according to any one of claims 1 to 3, further comprising: (F) an epoxy compound curing agent and / or a curing accelerator, and the total amount of the component (C) and the component (F) is 6 to 24 mass% based on the total mass of the solid content.

5. A photosensitive resin composition described in any one of claims 1 to 4, comprising the (G) colorant.

6. 6. The photosensitive resin composition according to claim 5, wherein the colorant (G) is a light-shielding material selected from the group consisting of a black organic pigment, a mixed-color organic pigment, or a black inorganic pigment.

7. The photosensitive resin composition according to any one of claims 1 to 6, comprising (H) silica particles, the silica particles having an average particle size of 1 to 95 nm as measured by a particle size distribution meter using a dynamic light scattering method by a cumulant method.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (D) is an acyloxime-based photopolymerization initiator having a molar absorption coefficient at 365 nm of 10,000 L / mol cm or more.

9. 9. The photosensitive resin composition according to claim 8, wherein the component (D) is an acyloxime-based photopolymerization initiator represented by general formula (5). 【Chemistry 6】 (R ６ , R ７ are each independently a C1 to C15 alkyl group, a C6 to C18 aryl group, a C7 to C20 arylalkyl group, or a C4 to C12 heterocyclic group; R ８ is a C1 to C15 alkyl group, a C6 to C18 aryl group, or a C7 to C20 arylalkyl group. Here, the alkyl group and the aryl group may be substituted with a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 alkanoyl group, or a halogen, and the alkylene portion may contain an unsaturated bond, an ether bond, a thioether bond, or an ester bond. The alkyl group may be any of linear, branched, and cyclic alkyl groups.

10. The photosensitive resin composition according to any one of claims 1 to 9, which is used for producing a cured film by post-baking at a temperature of 80 to 140°C.

11. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10.

12. A substrate having the cured film according to claim 11.

13. A method for producing a substrate with a cured film, comprising applying the photosensitive resin composition according to any one of claims 1 to 10 onto a substrate, exposing the composition through a photomask, removing unexposed areas by development, and heating the composition to form a cured film pattern.

Images