Photosensitive resin composition, hardened film, substrate with hardened film, and method for manufacturing substrate with hardened film

Abstract

The present application provides a photosensitive resin composition, a hardened film, a substrate with a hardened film, and a manufacturing method of a substrate with a hardened film, which can form a resin film pattern having excellent development adhesion, linearity, and resistance to solvents and alkalis, even when a substrate with low heat resistance is used. The photosensitive resin composition of the present application is a photosensitive resin composition for forming a hardened film on a substrate with a heat resistance temperature of 111°C or less, and comprises: (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable monomer having two or more ethylenic unsaturated bonds, (C) an epoxy compound having two or more 3,1-epoxycyclohexyl groups, (D) a photopolymerization initiator, and (E) a solvent. The content of the (C) component is 5 to 17 mass% relative to the total mass of the solid components.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a hardened film formed by curing the photosensitive resin composition, a substrate with the hardened film, and a method for manufacturing the substrate with the hardened film. Background Technology

[0002] In recent years, due to the need for flexible devices or one-chip devices, there has been a demand for the following: for example, the ability to directly form hardened film (transparent insulating film, etc.) patterns, colored film patterns, and light-shielding film patterns on plastic substrates (plastic films, resin films) such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN); and the ability to directly form hardened film patterns, colored film patterns, and light-shielding film patterns on substrates with organic devices, including organic electroluminescence (EL) or organic thin film transistors (TFT), on glass substrates or silicon wafers.

[0003] However, the heat resistance of the plastic substrate and the substrate with organic devices is as low as 111°C or below. Therefore, if existing photosensitive resin compositions are used to directly form resin film patterns, coloring film patterns, and light-shielding film patterns on the plastic substrate or the substrate with organic devices at a low calcination temperature of 111°C or below, the film strength of the formed patterns becomes insufficient, resulting in problems such as film reduction, surface roughness, and pattern peeling in subsequent processes (development processing, etc.).

[0004] Therefore, photosensitive resin compositions suitable for substrates with low heat resistance have been investigated. For example, Patent Document 1 discloses a radiosensitive linear composition containing an alkali-soluble resin of an acrylic copolymer, a photopolymerization initiator, and a thermal polymerization initiator. This radiosensitive linear composition, by including the photopolymerization initiator and the thermal polymerization initiator, enables the formation of a color filter with sufficient adhesion to the substrate even when calcined at a low temperature (111°C to 111°C) that does not cause yellowing.

[0005] [Existing Technical Documents]

[0006] [Patent Literature]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2113-15288 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] However, according to the insights of the inventors, although the radioactive linear composition described in Patent Document 1 has good adhesion to the substrate, it cannot obtain the desired development characteristics (e.g., pattern linewidth, pattern linearity) and solvent resistance.

[0010] The present invention has been made in view of the above aspects, and its object is to provide a photosensitive resin composition that can form a resin film pattern with excellent development adhesion, linearity and excellent solvent resistance and alkali resistance even when using a substrate with low heat resistance; a hardened film formed by curing the photosensitive resin composition; a substrate with the hardened film; and a method for manufacturing the substrate with the hardened film.

[0011] [Technical means to solve the problem]

[0012] The photosensitive resin composition of the present invention is a photosensitive resin composition for forming a hardened film on a substrate with a heat resistance temperature of 111°C or below, and comprises: (A) an alkali-soluble resin containing unsaturated groups, (B) a photopolymerizable monomer having at least two or more ethylene unsaturated bonds, (C) an epoxy compound having two or more 3,1-epoxycyclohexyl groups, (D) a photopolymerization initiator, and (E) a solvent, wherein the mass of component (C) is 5% to 17% by mass relative to the total mass of the solid components.

[0013] The hardened film of the present invention is formed by hardening the photosensitive resin composition.

[0014] The substrate with a hardening film of the present invention has the hardening film.

[0015] The method for manufacturing a substrate with a hardened film according to the present invention is a method for manufacturing a substrate with a hardened film by forming a hardened film pattern on a substrate with a heat resistance temperature of 111°C or below. In this method, the photosensitive resin composition is coated on the substrate and exposed through a light-blocking mask. The unexposed portion is removed by development and the hardened film pattern is formed by heating at 111°C or below.

[0016] [The effects of the invention]

[0017] According to the present invention, a photosensitive resin composition that can form a resin film pattern with excellent development adhesion, linearity, solvent resistance, and alkali resistance even when using a substrate with low heat resistance, a hardened film formed by curing the photosensitive resin composition, a substrate with the hardened film, and a method for manufacturing the substrate with the hardened film are provided. Detailed Implementation

[0018] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. Furthermore, in the present invention, when the first decimal place of the content of each component is 1, the description after the decimal point is sometimes omitted.

[0019] The alkali-soluble resin (A) containing unsaturated groups contained in the photosensitive resin composition of the present invention will be described.

[0020] The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin containing unsaturated groups. Any resin having an acid value for imparting alkali developability and suitable photocurability when combined with a photopolymerizable monomer of component (B) may be used without particular limitation.

[0021] Examples of the alkali-soluble resin (A) having a carboxyl group and a polymerizable unsaturated group within one molecule according to the present invention include the alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group within one molecule represented by general formula (3), said alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group within one molecule represented by general formula (3) is obtained by reacting an epoxy compound (a-1) having two epoxy groups within one molecule represented by general formula (6) with a reactant of a monocarboxylic acid containing an unsaturated group and a dicarboxylic acid or a tricarboxylic acid or their monoanhydride (b), and a tetracarboxylic acid or its dianhydride (c).

[0022] [Chemistry 1]

[0023]

[0024] (In formula (3), R1, R2, R3 and R1 are independently hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups, R5 is a hydrogen atom or a methyl group, A is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or a direct bond, Y is a tetravalent carboxylic acid residue, and Z are independently hydrogen atoms or substituents represented by general formula (1). Among them, one or more of Z are substituents represented by general formula (1), and n is an integer from 1 to 21.)

[0025] [Chemistry 2]

[0026]

[0027] (In formula (1), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0028] A detailed description is provided of the manufacturing method of an alkali-soluble resin (hereinafter also referred to as "alkali-soluble resin represented by general formula (3)") having a carboxyl group and a polymerizable unsaturated group within one molecule, as represented by general formula (3).

[0029] First, a monocarboxylic acid containing an unsaturated group (e.g., (meth)acrylic acid) is reacted with an epoxy compound (a-1) having two epoxy groups in one molecule, represented by general formula (6) (hereinafter also simply referred to as "epoxy compound (a-1) represented by general formula (6)"), to obtain a diol compound containing a polymerizable unsaturated group.

[0030] [Chemistry 3]

[0031]

[0032] (In formula (6), R1, R2, R3 and R1 are independently hydrogen atoms, alkyl atoms with 1 to 5 carbon atoms, halogen atoms or phenyl atoms, and A is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or direct bond.)

[0033] Epoxide (a-1) is an epoxy compound that has two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin.

[0034] Examples of bisphenols used as raw materials for epoxides (a-1) include: bis(1-hydroxyphenyl) ketone, bis(1-hydroxy-3,5-dimethylphenyl) ketone, bis(1-hydroxy-3,5-dichlorophenyl) ketone, bis(1-hydroxyphenyl) sulfone, bis(1-hydroxy-3,5-dimethylphenyl) sulfone, bis(1-hydroxy-3,5-dichlorophenyl) sulfone, bis(1-hydroxyphenyl)hexafluoropropane, bis(1-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(1-hydroxy-3,5-dichlorophenyl)hexafluoropropane, bis(1-hydroxyphenyl)dimethylsilane, bis(1-hydroxy-3,5-dimethylphenyl)dimethylsilane, bis(1-hydroxy-3,5-dichlorophenyl)dimethylsilane, bis(1-hydroxyphenyl)methane, bis(1-hydroxy-3,5-dichlorophenyl)methane, bis(1-hydroxy-3,5-dibromophenyl)methane, 2,2-bis(1-hydroxyphenyl)propane, 2,2-bis(1-hydroxy-3,5-dibromophenyl)methane 2,2-Dimethylphenyl)propane, 2,2-bis(1-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(1-hydroxy-3-methylphenyl)propane, 2,2-bis(1-hydroxy-3-chlorophenyl)propane, bis(1-hydroxyphenyl) ether, bis(1-hydroxy-3,5-dimethylphenyl) ether, bis(1-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis(1-hydroxyphenyl)fluorene, 9,9-bis(1-hydroxy-3-methylphenyl)fluorene, 9,9 9,9-bis(1-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(1-hydroxy-3-bromophenyl)fluorene, 9,9-bis(1-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(1-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(1-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(1-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(1-hydroxy-3,5-dibromophenyl)fluorene, 1,1'-biphenyl, 3,3'-biphenyl, etc. They can be used alone or in combination with two or more.

[0035] Examples of monocarboxylic acid compounds containing unsaturated groups include not only acrylic acid and methacrylic acid, but also compounds formed by reacting monoanhydrides such as succinic anhydride, maleic anhydride, and phthalic anhydride with acrylic acid or methacrylic acid.

[0036] The reaction of the epoxy compound (a-1) with (meth)acrylic acid can be carried out using known methods. For example, Japanese Patent Application Publication No. 1-355151 describes a method in which a diol compound containing polymerizable unsaturated groups is obtained by using approximately 2 moles of (meth)acrylic acid relative to 1 mole of an epoxy compound having two epoxy groups. In the present invention, the compound obtained by the reaction is a diol compound containing polymerizable unsaturated groups, and is a diol (d) containing polymerizable unsaturated groups represented by general formula (7) (hereinafter also simply referred to as "diol (d) represented by general formula (7)").

[0037] [Chemistry 1]

[0038]

[0039] (In formula (7), R1, R2, R3 and R1 are independently hydrogen atoms, alkyl atoms with 1 to 5 carbon atoms, halogen atoms or phenyl atoms, and A is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or direct bond.)

[0040] In the synthesis of diol (d) represented by general formula (7), the subsequent addition reaction of polycarboxylic acids or their anhydrides, and the reaction of monofunctional epoxy compounds having polymerizable unsaturated groups that are reactive with carboxyl groups to produce alkali-soluble resins represented by general formula (3), a catalyst is usually used in the solvent as needed to carry out the reaction.

[0041] Examples of solvents include: cellosol solvents such as ethyl cellosol acetate and butyl cellosol acetate; high-boiling-point ether or ester solvents such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and ketone solvents such as cyclohexanone and diisobutyl ketone. Furthermore, there are no particular restrictions on the reaction conditions regarding the solvents, catalysts, etc., used. For example, it is preferable to use a solvent that does not have hydroxyl groups and has a boiling point higher than the reaction temperature as the reaction solvent.

[0042] In addition, a catalyst is preferred in the reaction between the carboxyl group and the epoxy group. Japanese Patent Application Publication No. 9-325191 discloses ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride; and phosphines such as triphenylphosphine and tris(2,6-dimethoxyphenyl)phosphine.

[0043] Next, by reacting the diol (d) represented by general formula (7) obtained by reacting an epoxy compound (a-1) with (meth)acrylic acid, and a dicarboxylic acid or tricarboxylic acid or their monohydric anhydride (b), and a tetracarboxylic acid or its dianhydride (c), a base-soluble resin represented by general formula (3) having a carboxyl group and a polymerizable unsaturated group within one molecule can be obtained.

[0044] [Chemistry 5]

[0045]

[0046] (In formula (3), R1, R2, R3 and R1 are independently hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, halogen atoms or phenyl groups, R5 is a hydrogen atom or a methyl group, A is -CO-, -SO2-, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(CH3)2-, -O-, fluorene-9,9-diyl or a direct bond, Y is a tetravalent carboxylic acid residue, and Z are independently hydrogen atoms or substituents represented by general formula (1). Among them, one or more of Z are substituents represented by general formula (1), and n is an integer from 1 to 21.)

[0047] [Chemistry 6]

[0048]

[0049] (In formula (1), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2.)

[0050] The acid component used to synthesize the alkali-soluble resin represented by general formula (3) is a polybasic acid component that can react with the hydroxyl group in the diol (d) molecule represented by general formula (7), and requires the use of dicarboxylic acid or tricarboxylic acid or their monoanhydride (b) and tetracarboxylic acid or their dianhydride (c). The carboxylic acid residue of the acid component can be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. In addition, the carboxylic acid residue may also contain bonds containing heteroelements such as -O-, -S-, and carbonyl groups.

[0051] As dicarboxylic acids or tricarboxylic acids or their monohydric anhydrides (b), chain-type hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids, or their monohydric anhydrides, etc., can be used.

[0052] Examples of monoanhydrides of chain-type dicarboxylic or tricarboxylic acids include: succinic acid, acetylsuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citric acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, octanoic acid, diethylene glycol, etc., as well as monoanhydrides of dicarboxylic or tricarboxylic acids with any substituents. Examples of monoanhydrides of alicyclic dicarboxylic or tricarboxylic acids include: cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, etc., as well as monoanhydrides of dicarboxylic or tricarboxylic acids with any substituents. Examples of monoanhydrides of aromatic dicarboxylic or tricarboxylic acids include: phthalic acid, isophthalic acid, trimellitic acid, etc., as well as monoanhydrides of dicarboxylic or tricarboxylic acids with any substituents.

[0053] Among the monohydric anhydrides of dicarboxylic or tricarboxylic acids, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotriphenylamine, phthalic acid, and trimellitic acid are preferred, and succinic acid, itaconic acid, and tetrahydrophthalic acid are more preferred. Furthermore, among the dicarboxylic or tricarboxylic acids, their monohydric anhydrides are preferred. The monohydric anhydrides of the dicarboxylic or tricarboxylic acids may be used alone or in combination with two or more.

[0054] In addition, as a tetracarboxylic acid or its acid dianhydride (c), a chain-type hydrocarbon tetracarboxylic acid, an alicyclic hydrocarbon tetracarboxylic acid, an aromatic hydrocarbon tetracarboxylic acid, or their acid dianhydrides can be used.

[0055] Examples of chain-type tetracarboxylic acids include: butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and chain-type tetracarboxylic acids with substituents such as alicyclic hydrocarbon groups or unsaturated hydrocarbon groups. Examples of alicyclic tetracarboxylic acids include: cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, norbornanetetracarboxylic acid, and alicyclic tetracarboxylic acids with substituents such as chain hydrocarbon groups or unsaturated hydrocarbon groups. Examples of aromatic tetracarboxylic acids include: pyromellitic tetracarboxylic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenyl sulfone tetracarboxylic acid.

[0056] Among the tetracarboxylic acids or their dianhydrides, biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid, and diphenyl ether tetracarboxylic acid are preferred, and biphenyltetracarboxylic acid and diphenyl ether tetracarboxylic acid are more preferred. Furthermore, among the tetracarboxylic acids or their dianhydrides, their dianhydrides are preferred. In addition, the tetracarboxylic acid or its dianhydride may be used alone or in combination with two or more.

[0057] There are no particular limitations on the reaction of the diol (d) represented by general formula (7) with acid components (b) and (c), and known methods can be used. For example, Japanese Patent Application Publication No. 9-325191 describes a method for reacting (meth)acrylate epoxy ester with tetracarboxylic acid dianhydride at a reaction temperature of 91°C to 111°C.

[0058] Here, in order to make the end of the compound a carboxyl group, it is preferred to carry out the reaction in such a way that the molar ratio of the diol (d), dicarboxylic acid or tricarboxylic acid or their monohydric anhydride (b), tetracarboxylic acid or their dianhydride (c) represented by general formula (7) is (d):(b):(c) = 1:1.11 to 1.1:1.2 to 1.1.

[0059] For example, when using (b) acid monohydric anhydride and (c) acid dianhydride, it is preferable to carry out the reaction in such a way that the amount of acid component [(b) / 2+(c)] relative to the molar ratio of the diol (d) represented by general formula (7) [(d) / [(b) / 2+(c)]] is 1.5 to 1.1. Here, when the molar ratio is 1.1 or less, the content of the diol compound containing unreacted polymeric unsaturated groups will not increase, thus improving the long-term stability of the alkali-soluble resin composition. On the other hand, when the molar ratio exceeds 1.5, since the end of the alkali-soluble resin represented by general formula (3) will not become anhydride, the increase in the content of unreacted acid dianhydride can be suppressed, thus improving the long-term stability of the alkali-soluble resin composition. Furthermore, the molar ratio of each component of (d), (b), and (c) can be arbitrarily changed within the range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by general formula (3).

[0060] Furthermore, the preferred range for the acid value of the alkali-soluble resin represented by general formula (3) is 21 mg KOH / g to 181 mg KOH / g, preferably 81 mg KOH / g or higher and 121 mg KOH / g or lower. When the acid value is 21 mg KOH / g or higher, residue is less likely to remain during alkaline development; when the acid value is 181 mg KOH / g or lower, the penetration of the alkaline developer does not become too rapid, thus suppressing peeling. In addition, the acid value can be determined using a potentiometric titration apparatus "COM-1611" (manufactured by Hiranuma Sangyo Co., Ltd.) and by titration with a 1 / 11 N-KOH aqueous solution.

[0061] The weight-average molecular weight (Mw) of the polystyrene obtained by gel permeation chromatography (GPC) of the alkali-soluble resin represented by general formula (3) (HLC-8221GPC, manufactured by Tosoh Corporation) is typically 1111 to 111111, preferably 2111 to 21111, and more preferably 2111 to 6111. When the weight-average molecular weight is 1111 or higher, the reduction in pattern adhesion during alkaline development can be suppressed. In addition, when the weight-average molecular weight is less than 111111, the solution viscosity of the photosensitive resin composition, which is preferred for coating, can be easily adjusted, and alkaline development will not require excessive time.

[0062] When the coloring material is not included, the content of component (A) in the photosensitive resin composition of the present invention is preferably 31% to 81% by mass relative to the total mass of the solid components, and preferably 2% or more and 71% or less when the coloring material is included.

[0063] The photosensitive resin composition of the present invention comprises (B) a photopolymerizable monomer having at least two vinyl unsaturated bonds. Component (B) further improves the adhesion of the hardened film and, in addition, improves the solubility of the exposed portion relative to the alkaline developer, thereby further improving the linear reproducibility of the hardened film. However, in order to prevent the hardened film from becoming brittle and to suppress the decrease in the acid value of the composition, improve the solubility of the unexposed portion relative to the alkaline developer, and further improve the linear reproducibility of the hardened film, the amount of component (B) is preferably not excessive.

[0064] Examples of photopolymerizable monomers (B) having at least two vinyl 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)propane... Acrylates, dipentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxy-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and other (meth)acrylates; dendritic polymers containing (meth)acryloyl groups as compounds with vinyl double bonds, etc. Furthermore, they can be used alone or in combination with two or more.

[0065] Examples of dendritic polymers having (meth)acryloyl groups as compounds having ethylene double bonds include dendritic polymers obtained by adding a portion of the carbon-carbon double bond in the (meth)acryloyl group of a polyfunctional (meth)acrylate to a polythiol compound. Specifically, it includes dendritic polymers obtained by reacting the (meth)acryloyl group of a polyfunctional (meth)acrylate represented by general formula (8) with the thiol group of a polythiol compound represented by general formula (9).

[0066] [Chemistry 7]

[0067]

[0068] (In formula (8), R9 is a hydrogen atom or a methyl group, R 11 It is R 11 (OH) k One of the k hydroxyl groups is supplied to the residual portion after the ester bond in the formula. R is preferred. 11 (OH) k, is a polyol with a non-aromatic straight-chain or branched hydrocarbon skeleton having 2 to 8 carbon atoms, or a polyol ether formed by the dehydration condensation of multiple molecules of the polyol and the linkage via ether bonds, or an ester of the polyol or polyol ether with a hydroxy acid. k and l are independently integers from 2 to 21, k ≥ l.

[0069] [Chemistry 8]

[0070]

[0071] (In equation (9), R) 12 It is a single bond or a C1-C6 hydrocarbon group with a divalent to hexavalent valence, in R 12 When it is a single bond, p is 2, and in R 12 (For base values ​​of 2 to 6, p is an integer from 2 to 6.)

[0072] Examples of polyfunctional (meth)acrylates represented by 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, 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, and tripentaerythritol hepta(meth)acrylate. The following compounds are included: 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, hydroxypentanoic 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, trimethylolpropane benzoate (meth)acrylate, tri((meth)acryloyloxyethyl)isocyanurate, alkoxy-modified trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, alkyl-modified dipentaerythritol tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, etc. Each compound may be used alone or in combination with two or more.

[0073] Examples of polythiol compounds represented by general formula (9) include: 1,2-dimercaptoethane, 1,3-dimercaptopropane, 1,1-dimercaptobutane, bis(dimercaptoethanethiol), trimethylolpropane tris(thioacetate), trimethylolpropane tris(thiopropionate), pentaerythritol tetras(thioacetate), pentaerythritol tris(thioacetate), pentaerythritol tetras(thiopropionate), dipentaerythritol hexas(thioacetate), dipentaerythritol hexas(thiopropionate), etc. The compounds may be used alone or in combination with two or more.

[0074] Additionally, polymerization inhibitors may be added as needed during the synthesis of the dendritic polymer. Examples of polymerization inhibitors include hydroquinone-based compounds and phenolic compounds. Specific examples include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, butylated hydroxytoluene, 2,1,6-tri-tert-butylphenol (BHT), etc.

[0075] The mixing ratio of component (A) to component (B), by weight (A) / (B), is preferably 31 / 71 to 91 / 11, more preferably 61 / 11 to 81 / 21. If the mixing ratio of component (A) is 31 / 71 or higher, the cured film after photocuring is less likely to become brittle. Furthermore, the acid value of the coating in the unexposed area is less likely to decrease, thus suppressing a decrease in solubility relative to the alkaline developer. This prevents defects such as jagged edges or dullness of the pattern. Conversely, if the mixing ratio of component (A) is 91 / 11 or lower, the proportion of photoreactive functional groups in the resin is sufficient, allowing for the formation of the desired cross-linked structure. Additionally, since the acid value of the resin component is not too high, the solubility of the exposed area relative to the alkaline developer is less likely to increase, thus preventing the formed pattern from becoming thinner than the target line width or suppressing pattern defects.

[0076] The photosensitive resin composition of the present invention comprises (C) an epoxy compound having a 3,1-epoxycyclohexyl group. Examples of (C) epoxy compounds having a 3,1-epoxycyclohexyl group include epoxy compounds represented by general formula (1) or general formula (2).

[0077] [Chemistry 9]

[0078]

[0079] (In formula (1), X is a single bond or a divalent organic group with 1 to 21 carbon atoms that may contain heteroatoms.)

[0080] [Chemistry 11]

[0081]

[0082] (In equation (2), a, b, c, and d are each 1 or 1 independently, and a+b+c+d = 1 to 3).

[0083] Here, X in the epoxy compound represented by general formula (1) is a single bond or a divalent organic group with 1 to 21 carbon atoms that may contain heteroelements. Examples of divalent organic groups with 1 to 21 carbon atoms that may contain heteroelements include: divalent hydrocarbon groups, divalent groups having carboxyl groups at one or both ends of the hydrocarbon group, etc. In addition, the hydrocarbon group may also have an ether-bonded oxygen atom or an ester bond inside.

[0084] Examples of the divalent hydrocarbon group include straight-chain hydrocarbon groups such as methylene, ethylene, propylene, isopropylene, sec-butenyl, methylisobutylenyl, hexenyl, decenyl, and dodecenyl. Examples of divalent groups having a carboxyl group at the end of the hydrocarbon group include divalent organic groups represented by general formulas (11) to (13). Preferably, in general formula (11), g is 1; in general formula (11), h is 5 and i is 1; in general formula (12), j is 2; and in general formula (13), k is 1 and l is 1.

[0085] [Chemistry 11]

[0086]

[0087] (In equation (11), g is an integer from 1 to 21.)

[0088] [Chemistry 12]

[0089]

[0090] (In equation (11), h is an integer from 2 to 21, and i is an integer from 1 to 11.)

[0091] [Chemistry 13]

[0092]

[0093] (In equation (12), j is an integer from 1 to 21.)

[0094] [Chemistry 11]

[0095]

[0096] (In equation (13), k is an integer from 1 to 18, and l is an integer from 1 to 11.)

[0097] Furthermore, examples of epoxy compounds represented by general formula (1) include epoxy compounds represented by general formulas (11) to (21). Two or more epoxy compounds may be used simultaneously. Among the epoxy compounds represented by general formulas (11) to (21), epoxy compounds represented by general formulas (17) or (18) are preferred in terms of ease of acquisition and the physical properties of the cured film, where g is 1, h is 5, and i is 1.

[0098] [Chemistry 15]

[0099]

[0100] [Chemistry 16]

[0101]

[0102] [Chemistry 17]

[0103]

[0104] [Chemistry 18]

[0105]

[0106] (In equation (17), g is an integer from 1 to 21.)

[0107] [Chemistry 19]

[0108]

[0109] (In equation (18), h is an integer from 2 to 21, and i is an integer from 1 to 11.)

[0110] [Chemistry 21]

[0111]

[0112] (In equation (19), j is an integer from 1 to 21.)

[0113] [Chemistry 21]

[0114]

[0115] (In equation (21), k is an integer from 1 to 18, and l is an integer from 1 to 11.)

[0116] The content of epoxy compound in component (C) is preferably 5% to 17% by mass relative to the total mass of the solid components. By making the content of epoxy compound in component (C) 5% by mass or more, solvent resistance can be achieved; by making the content of epoxy compound in component (C) 17% by mass or less, solvent resistance can be achieved, and the adhesion between the pattern and the substrate can be sufficiently ensured.

[0117] Furthermore, in component (C), an epoxy compound represented by general formula (2) is preferred. By using an epoxy compound represented by general formula (2) that has one epoxy cyclohexyl group in the molecule, the solvent resistance of the hardened film (coating) can be improved even without the use of a hardener and a hardening accelerator.

[0118] The epoxy equivalent of component (C) is preferably 111 g / eq to 311 g / eq. Furthermore, the number average molecular weight (Mn) of the epoxy compound in component (C) is preferably 111 to 5111. If the epoxy equivalent is 111 g / eq to 311 g / eq and the number average molecular weight (Mn) of the epoxy compound is 111 to 5111, then good adhesion during development can be ensured, and a hardened film with good solvent resistance can be formed. Alternatively, if the epoxy equivalent is 311 g / eq or less, a photosensitive resin composition with an appropriate development speed can be designed, and the solvent resistance of the hardened film can also be ensured. Furthermore, it is more preferable to use an epoxy compound having three or more epoxy groups in one molecule. In addition, only one of these compounds may be used, or two or more may be used in combination.

[0119] The photosensitive resin composition of the present invention comprises (D) a photopolymerization initiator.

[0120] Examples of ingredients (D) include: acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and other acetophenone derivatives; benzophenone, 2-chlorobenzophenone, p,p'-bis(dimethylaminobenzophenone), and other benzophenone derivatives; benzoin ethers such as benzoyl, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-(o-chlorophenyl)-1,5-phenylbiimidazole, 2-(o-chlorophenyl)-1,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-1,5-diphenylbiimidazole, 2-(o-methoxyphenyl)-1,5-diphenylbiimidazole, and 2,1,5-triarylbiimidazole. Biimidazole compounds such as azoles; halogenated methyldiazole compounds such as 2-trichloromethyl-5-styryl-1,3,1-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,1-oxadiazole, and 2-trichloromethyl-5-(p-methoxystyryl)-1,3,1-oxadiazole; 2,1,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-1,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-1,6-bis(trichloromethyl)-1,3,5-triazine, 2-(1-chlorophenyl)-1,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(1-methoxyphenyl)-1,6-bis(trichloromethyl)-1,3,5- Triazine, 2-(1-methoxynaphthyl)-1,6-bis(trichloromethyl)-1,3,5-triazine, 2-(1-methoxystyryl)-1,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,1,5-trimethoxystyryl)-1,6-bis(trichloromethyl)-1,3,5-triazine, 2-(1-methylthiostyryl)-1,6-bis(trichloromethyl)-1,3,5-triazine, and other halomethyl-triazine compounds; 1,2-octanedione, 1-[1-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(1-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoate, 1-(1-methylthiophenyl)butane O-acyl oxime compounds such as alkyl-1,2-dione-2-oxime-O-acetate and 1-(1-methylthiophenyl)butane-1-one-oxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthones, 2-chlorothioxanthones, 2,1-diethylthioxanthones, 2-methylthioxanthones, and 2-isopropylthioxanthones; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, and cumene peroxide; thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, and pentaerythritol tetra(3-mercaptopropionate); and tertiary amines such as triethanolamine and triethylamine. Furthermore, the photopolymerization initiator can be used alone or in combination with two or more.

[0121] Especially when the composition is a photosensitive resin containing a coloring material, it is preferable to use O-acyl oxime compounds (including ketoximes). Specific examples of the compound group include O-acyl oxime photopolymerization initiators represented by general formula (5) or general formula (21). Among the compound group, when the coloring material is used at a high pigment concentration and when forming a light-shielding film pattern, it is preferable to use an O-acyl oxime photopolymerization initiator with a molar absorptivity of 11111 L / mol·cm or higher at 365 nm. Furthermore, the term "photopolymerization initiator" as used in this invention is used in the sense that it includes a sensitizer.

[0122] [Chemistry 22]

[0123]

[0124] (In formula (5), R6 and R7 are independently C1-C15 alkyl, C6-C18 aryl, C7-C21 arylalkyl, or C1-C12 heterocyclic groups, respectively, and R8 is C1-C15 alkyl, C6-C18 aryl, or C7-C21 arylalkyl. Here, the alkyl and aryl groups can be substituted by C1-C11 alkyl, C1-C11 alkoxy, C1-C11 alkanoyl, or halogens, and the alkylene moiety can contain unsaturated bonds, ether bonds, thioether bonds, or ester bonds. In addition, the alkyl group can be any type of straight-chain, branched, or cyclic alkyl group.)

[0125] [Chemistry 23]

[0126]

[0127] (In equation (21), R) 13 and R 11 Each is independently a straight-chain or branched alkyl group having 1 to 11 carbon atoms, or a cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl group having 1 to 11 carbon atoms, or a phenyl group that can be substituted by an alkyl group having 1 to 6 carbon atoms. R 15 Independently, it is a straight-chain or branched alkyl or alkenyl group having 2 to 11 carbon atoms, wherein a portion of the -CH2- group in the alkyl or alkenyl group may be substituted with an -O- group. Furthermore, the R... 13 ~R 15 (Some of the hydrogen atoms in the radical can also be replaced by halogen atoms.)

[0128] The content of component (D) is preferably 1.1% to 31% by mass, more preferably 1% to 25% by mass, relative to the total mass of components (A) and (B). If the content of component (D) is 1.1% by mass or more, a suitable photopolymerization rate is achieved, thus suppressing the decrease in sensitivity. Furthermore, if the content of component (D) is 31% by mass or less, linewidths faithful to the mask can be reproduced, and pattern edges can be sharpened.

[0129] The photosensitive resin composition of the present invention comprises (E) solvent.

[0130] (E) Examples of solvents contained in the 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-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; and cellosolves, methyl cellosolves, ethyl cellosolves, carbitol, methyl carbitol, ethyl carbitol, and butyl carbitol. Diol ethers such as diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, ethyl lactate, 3-methoxy-butyl acetate, 3-methoxy-3-butyl acetate, cellolytic acetate, ethyl cellolytic acetate, butyl cellolytic acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. By dissolving and mixing these solvents, a homogeneous solution composition can be prepared. To obtain necessary properties such as coatability, the solvents can be used alone or in combination of two or more.

[0131] The content of component (E) varies depending on the target viscosity, but is preferably 61% to 91% by mass in the photosensitive resin composition solution.

[0132] The photosensitive resin composition of the present invention may contain a curing agent and / or curing accelerator of an epoxy compound (F). When the photosensitive resin composition of the present invention is a composition calcined at a low temperature below 111°C, the curing of component (C) is prone to be insufficient. Therefore, the photosensitive resin composition preferably contains component (F) in order to ensure sufficient curing of component (C).

[0133] Examples of curing agents for epoxy compounds as component (F) include: amine compounds, polycarboxylic acid compounds, phenolic resins, amino resins, dicyandiamine, Lewis acid complex compounds, etc. Polycarboxylic acid compounds are preferably used in this invention.

[0134] Examples of polycarboxylic acid compounds include: polycarboxylic acids, anhydrides of polycarboxylic acids, and thermally decomposable esters of polycarboxylic acids. A polycarboxylic acid is a compound having two or more carboxyl groups in one molecule. Examples include: succinic acid, maleic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclohexene-1,5-dicarboxylic acid, norbornane-2,3-dicarboxylic acid, phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, benzene-1,2,1-tricarboxylic acid, cyclohexane-1,2,1-tricarboxylic acid, benzene-1,2,1,5-tetracarboxylic acid, cyclohexane-1,2,1,5-tetracarboxylic acid, butane-1,2,3,1-tetracarboxylic acid, etc. Examples of anhydrides of polycarboxylic acids include the anhydrides of the above compounds. These can be intermolecular anhydrides, but intramolecularly closed-ring anhydrides are commonly used. Examples of thermally decomposable esters of polycarboxylic acids include tert-butyl esters, 1-(alkyloxy)ethyl esters, and 1-(alkylthio)ethyl esters of the compounds mentioned above (wherein the alkyl group is a saturated or unsaturated hydrocarbon group having 1 to 21 carbon atoms, and the hydrocarbon group may have a branched or cyclic structure and may be substituted by any substituent). Additionally, polymers or copolymers having two or more carboxyl groups may also be used as polycarboxylic acid compounds, where the carboxyl groups may be anhydrides or thermally decomposable esters.

[0135] Furthermore, examples of the polymers or copolymers include: polymers or copolymers containing (meth)acrylic acid as a constituent, copolymers containing maleic anhydride as a constituent, and compounds in which the anhydride is ring-opened by reacting a tetracarboxylic dianhydride with a diamine or diol. Among these compounds, the anhydrides of phthalic acid, 3,6-dihydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, methyltetrahydrophthalic acid, and phenyl-1,2,1-tricarboxylic acid are preferably used. Regarding the formulation ratio when using a polycarboxylic acid compound as a curing agent for an epoxy compound, it is preferable to formulate the compound such that, for every 1 mole of the epoxy group of the epoxy compound, the carboxyl group of the polycarboxylic acid compound is 1.5 to 1.1 moles, more preferably 1.6 to 1.95 moles.

[0136] The curing accelerator for the epoxy compound as component (F) can be a known compound that is a curing accelerator, curing catalyst, or potential curing agent for epoxy compounds. Examples of curing accelerators for epoxy compounds include: tertiary amines, quaternary ammonium salts, tertiary phosphine, quaternary phosphonium salts, borate esters, Lewis acids, organometallic compounds, imidazoles, etc. Among the curing accelerators, 1,8-diazabicyclo[5.1.1]undec-7-ene or 1,5-diazabicyclo[1.3.1]non-5-ene or their salts are preferred.

[0137] The amount of curing accelerator added is preferably 1.15 to 2 parts by weight relative to 111 parts by weight of epoxy compound, and the amount can be adjusted according to the chemical resistance of the resin film pattern after heat curing.

[0138] Furthermore, relative to the total mass of the solid components, the combined mass of component (C) and component (F) is preferably 6% to 21% by mass, more preferably 8% to 22% by mass. By including sufficient amounts of component (C) and component (F), the linewidth reproducibility, linear reproducibility, and solvent resistance of the formed hardened film can be significantly improved.

[0139] In addition, the equivalent number E of the epoxy groups in component (C) ep The ratio of the equivalent number of the curing agent to the epoxy compound of component (F) is preferably E. ep / Hardener = 1.5~2.5. If E ep When the hardener content is 1.5 or higher, the epoxy compound can be fully cured, thus preventing unreacted epoxy compounds from remaining in the photosensitive resin composition. Additionally, if E... ep When the hardener content is below 2.5, the adhesion and linear reproducibility of the hardened film can be significantly improved.

[0140] The photosensitive resin composition of the present invention may contain (G) a coloring material.

[0141] The coloring material is preferably a coloring material 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 coloring material as component (G) can be arbitrarily determined according to the desired light-shielding degree, and is preferably 21% to 81% by mass relative to the solid content in the photosensitive resin composition, more preferably 11% to 71% by mass. If the coloring material is 21% by mass or more relative to the solid content in the photosensitive resin composition, sufficient light-shielding properties can be obtained. If the coloring material is 81% by mass or less relative to the solid content in the photosensitive resin composition, the content of the original photosensitive resin as a binder will not decrease, and therefore the desired development characteristics and film-forming ability can be obtained.

[0142] Examples of black organic pigments as component (G) include perylene black, cyanine black, aniline black, and lactam black. Examples of mixed organic pigments include pigments formed by mixing at least two colors selected from organic pigments such as azo pigments, condensed azo pigments, azomethyl alkali pigments, phthalocyanine pigments, quinacridone pigments, isoindolineone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinoline phthaloline pigments, diketopyrrolopyrrole pigments, and thioindigo pigments, and then simulating blackening. Black inorganic pigments include carbon black, chromium oxide, iron oxide, and titanium black. Depending on the function of the target photosensitive resin composition, component (G) may be used alone or in combination with two or more. Among the pigments, carbon black is preferred from the viewpoints of opacity, surface smoothness, dispersion stability, and affinity with the resin. Furthermore, when using organic pigments, in order to achieve microdispersion with an average particle size of less than 51 nm, organic pigments that have undergone micronization processing (with a specific surface area of ​​51 nm based on the Brunauer-Emmett-Teller (BET) method) are preferred. 2 Organic pigments (at least / g).

[0143] Examples of organic pigments that can be used as component (G) include, but are not limited to, pigments numbered as follows in the Color Index.

[0144] Pigment Red (2, 3, 1, 5, 9, 12, 11, 22, 23, 31, 38, 112, 122, 111, 116, 117, 119, 166, 168, 171, 175, 176, 177, 178, 179, 181, 185, 187, 188, 212, 217, 218, 219, 211, 213, 211, 221, 221, 212, 217, 253, 251, 255, 256, 257, 262, 261, 266, 272, 279, etc.)

[0145] Pigment orange (5, 13, 16, 31, 36, 38, 13, 61, 62, 61, 67, 68, 71, 72, 73, 71, 81, etc.)

[0146] Pigment yellow (1, 3, 12, 13, 11, 16, 17, 55, 73, 71, 81, 83, 93, 95, 97, 119, 111, 111, 117, 121, 126, 127, 128, 129, 131, 136, 138, 139, 151, 151, 153, 151, 155, 173, 171, 175, 176, 181, 181, 183, 185, 191, 191, 199, 213, 211, etc.)

[0147] Pigment green (7, 36, 58, etc.)

[0148] Pigment blue in ratios of 15, 15:1, 15:2, 15:3, 15:1, 15:6, 16, 61, and 81, etc.

[0149] Pigment violet (19, 23, 37, etc.)

[0150] Furthermore, the coloring material of component (G) is preferably pre-dispersed with a dispersant in a solvent to prepare a coloring material dispersion, which is then formulated as a photosensitive resin composition for use as a coloring film. Here, the solvent used for dispersion can be the aforementioned solvent. Among the solvents, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc., are preferred.

[0151] The dispersant can be any known dispersant, such as various polymeric dispersants. Examples of dispersants include, without particular limitation, compounds known for their use in existing pigment dispersions (compounds commercially available under names such as dispersant, dispersing wetting agent, and dispersing accelerator). Examples of such dispersants include: cationic polymeric dispersants, anionic polymeric dispersants, nonionic polymeric dispersants, and pigment derivative-type dispersants (dispersing aids). Particularly regarding pigment adsorption, cationic polymeric dispersants having cationic functional groups such as imidazole, pyrrole, pyridinyl, primary amino, secondary amino, or tertiary amino groups, with an amine value of 1 mg KOH / g to 111 mg KOH / g and a number average molecular weight of 1,000 to 110,000 are preferred. The amount of the dispersant prepared is preferably 1% to 31% by mass, more preferably 2% to 25% by mass, relative to the coloring material.

[0152] Furthermore, in preparing the coloring material dispersion, not only the dispersant but also a portion of the alkali-soluble resin containing polymeric unsaturated groups of component (A) can be co-dispersed. By co-dispersing a portion of the alkali-soluble resin containing polymeric unsaturated groups of component (A), a photosensitive resin composition that easily maintains high exposure sensitivity, exhibits good adhesion during development, and is less prone to residue formation can be produced. In the coloring material dispersion, the amount of component (A) is preferably 2% to 21% by mass, more preferably 5% to 15% by mass. If component (A) is 2% by mass or more, the effects of improved sensitivity, improved adhesion, and reduced residue due to co-dispersion can be obtained. If component (A) is 21% by mass or less, especially when the content of coloring material is high, the viscosity of the coloring material dispersion will not become excessively high, and it can be uniformly dispersed. The obtained coloring material dispersion can be mixed with components (A) to (F) and other components can be added as needed and the viscosity adjusted to be suitable for film-forming conditions to produce the photosensitive resin composition used in the manufacturing method of the present invention.

[0153] The photosensitive resin composition of the present invention preferably contains (H) silica particles.

[0154] Regarding the silica particles used as the (H) component, there are no particular restrictions on the manufacturing method, such as gas-phase reaction or liquid-phase reaction, or on their shape (spherical or non-spherical). Furthermore, silica particles that have undergone surface treatment, such as treatment with a silane coupling agent, can also be used without particular restriction.

[0155] The type of silica particles used as component (H) in this invention is not particularly limited. Solid silica or hollow silica particles can be used. Furthermore, "hollow silica particles" refers to silica particles with cavities inside.

[0156] By using the silica particles, the refractive index of the light-shielding film containing the silica particles can be reduced.

[0157] The average particle size of the silica particles is preferably 1 nm to 95 nm, more preferably 5 nm to 91 nm. By using silica particles with a small average particle size, the formation of jagged edges on the sides of the fine line pattern can be suppressed. In addition, it has the effect of reducing the unevenness of the surface of the hardened film (coating) and suppressing the deviation of reflectivity within the surface of the hardened film (coating).

[0158] Furthermore, the content of the silica particles is preferably 1.1% to 5% by mass, more preferably 1.1% to 2% by mass, relative to the total mass of the photosensitive resin composition. If the content of the silica particles is within this range, low reflectivity can be achieved while ensuring good patternability.

[0159] The average particle size of the silica particles can be determined using a particle size analyzer, "Particle Size Analyzer FPAR-1111" (manufactured by Otsuka Electronics Co., Ltd.), employing a dynamic light scattering method, and by using an accumulation method.

[0160] Furthermore, the refractive index of the silica particles can be between 1.11 and 1.17. Not only can ordinary silica particles with a refractive index of 1.15 to 1.17 be used, but hollow silica particles with a low refractive index can also be used, thereby further reducing the refractive index of the light-shielding film compared to that of a light-shielding film containing only ordinary silica particles.

[0161] Furthermore, the refractive index of silica particles can be determined from a transparent mixture obtained by mixing silica particles, which are processed into powder, with a standard refractive liquid of known refractive index. In this case, the refractive index of the standard refractive liquid is set as the refractive index of the silica particles. Additionally, the refractive index of the silica particles can be measured using an Abbe refractometer.

[0162] In addition, it can suppress reflection caused by the difference in refractive index between the layer formed on the hardened film (coating) and the hardened film (coating). Therefore, even without setting an anti-reflection film, reflection can be suppressed.

[0163] The silica particles can be spherical or elliptical in shape. The silica particles used in this invention are preferably spherical.

[0164] The sphericity of the silica particles is preferably 1.1 to 1.5. If the sphericity of the silica particles is within this range, the particle shape is close to spherical. Therefore, they can be homogeneously filled into a thin-film light-shielding film, forming a light-shielding film that maintains the smoothness of the film surface while preventing the silica particles from protruding from the film surface. Thus, a light-shielding film with low refractive index and sufficient strength can be obtained. In obtaining such a light-shielding film that achieves low reflection on the film surface, the selection of the photopolymerization initiator is also an important factor. It is preferable to use an oxime ester-based photopolymerization initiator commonly used in light-shielding films, and to add 1.5% to 5% of a thiol compound in the solid component.

[0165] The sphericity of the silica particles can be determined by the ratio of the longest diameter to the shortest diameter of the particles (the average of any 111 silica particles). Here, the longest and shortest diameters of the silica particles are obtained by photographing the silica particles using a transmission electron microscope and measuring the longest and shortest diameters of the silica particles based on the obtained microscope images.

[0166] The silica particles, which are the component (H), can be mixed with other formulation components as a silica particle dispersion formed by dispersing in a solvent. The dispersant can be any known compound used in the dispersion of pigments (opacifying components), such as commercially available compounds under names like dispersant, dispersing wetting agent, or dispersing accelerator.

[0167] The photosensitive resin composition of the present invention may be formulated with thermal polymerization inhibitors and additives such as antioxidants, plasticizers, fillers, leveling agents, defoamers, surfactants, and coupling agents as needed. Examples of thermal polymerization inhibitors and antioxidants include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenolic compounds. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silica, mica, and alumina. Examples of defoamers or leveling agents include silicone-based, fluorinated, and acrylic compounds. Examples of surfactants include fluorinated surfactants and silicone surfactants. Examples of coupling agents include: 3-(glycidoxy)propyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, 3-ureopropyltriethoxysilane, etc.

[0168] The method for manufacturing the curing film of the present invention is as follows: the photosensitive resin composition is coated on a substrate with a heat resistance temperature of 111°C or below, and exposed through a light mask; the unexposed portion is removed by development; and the film is heated at 111°C or below to form a predetermined curing film pattern.

[0169] Examples of substrates used in the manufacturing method of the hardened film of the present invention include resin films (plastic substrates) such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) with a heat resistance temperature of 111°C or below; substrates on which electrodes such as indium tin oxide (ITO) or gold are deposited or patterned on the resin film are also included within the category of substrates. Here, "heat resistance temperature" refers to the temperature at which, even if the substrate is exposed during processing such as patterning the hardened film on the substrate, problems such as deformation will not occur. Furthermore, although the temperature of the resin film varies depending on the degree of stretching treatment, it must not exceed the glass transition temperature (Tg).

[0170] Furthermore, examples of other substrates used in the manufacturing method of the curing film of the present invention include substrates with high inherent heat resistance, such as glass substrates, silicon wafers, and polyimide films, but on which a film with low heat resistance is formed. Specific examples of other substrates include substrates with organic devices, such as glass substrates, silicon wafers, or polyimide films, on which organic EL (Organic Light-Emitting Diode, OLED) or organic thin-film transistor (TFT) devices are formed. Furthermore, the heat resistance temperature of the substrate with low heat resistance, which is the target of the present invention, varies depending on the type of resin or the device, but is preferably 81°C to 111°C. Moreover, the substrate with organic devices also includes substrates on which a protective film or similar material is formed after the organic device is formed. This is because even if the heat resistance of the protective film or similar material itself is 151°C or higher, in order to ensure the function of the organic device, the heat resistance is essentially only 111°C or lower; in this case, it is equivalent to a substrate with organic devices.

[0171] As a method for coating the photosensitive resin composition of the present invention onto a substrate, not only known solutions impregnation and spraying methods can be used, but also any method using a roller coater, a land coater, a slot coater, or a rotary coater. After coating to the desired thickness using the method described above, the solvent is removed (pre-baking), thereby forming a film. Pre-baking is performed by heating using an oven, a heating plate, or the like. The heating temperature and heating time during pre-baking can be appropriately selected depending on the solvent used, for example, at a temperature of 61°C to 111°C (set in a manner that does not exceed the heat resistance temperature of the substrate) for 1 to 3 minutes.

[0172] The exposure following pre-baking is performed using an ultraviolet (UV) exposure device with a photomask, thus exposing only the resist corresponding to the pattern. Suitable exposure devices and conditions are selected, and light sources such as ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, or far-ultraviolet lamps are used for exposure, thereby photocuring the photosensitive resin composition in the coating. Preferably, photocuring is performed by irradiating a specific amount of light with a wavelength of 365 nm.

[0173] The radiation used in the exposure can be, for example, visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc., with a wavelength range preferably between 251 nm and 151 nm. Additionally, suitable developing solutions for alkaline development include, for example, aqueous solutions of sodium carbonate, potassium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, etc. The developing solution can be appropriately selected based on the characteristics of the resin layer, but surfactants may be added as needed. The developing temperature is preferably between 21°C and 35°C, allowing for the precise formation of fine images using commercially available developing machines or ultrasonic cleaners. Furthermore, water washing is typically performed after alkaline development. As developing methods, spray developing, immersion developing, and puddle developing methods can be applied.

[0174] Alkaline development after exposure is performed to remove the resist from the unexposed areas, thereby forming the desired pattern. Examples of suitable developing solutions for alkaline development include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, etc. Particularly preferred is a weakly alkaline aqueous solution containing 1.15% to 3.1% by mass of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, developed at a temperature of 23°C to 28°C. Furthermore, commercially available developing machines or ultrasonic cleaners can be used to precisely form fine images.

[0175] After development, heat treatment (post-baking) is preferably performed at a temperature of 81°C to 111°C (set in a way that does not exceed the heat resistance temperature of the substrate) for 21 to 91 minutes, more preferably at a temperature of 91°C to 121°C for 31 to 61 minutes. The post-baking is performed to improve the adhesion between the patterned hardened film and the substrate. It is performed similarly to pre-baking by heating using an oven, heating plate, or the like. The patterned resin film of the present invention is formed through the above-described photolithography processes.

[0176] [Example]

[0177] The embodiments and comparative examples of the present invention will be described in detail below, but the present invention is not limited to the embodiments and comparative examples described.

[0178] First, the description will begin with an example of the synthesis of an alkali-soluble resin containing a polymerizable unsaturated group as represented by general formula (3), and unless otherwise described, the resin in the example will be evaluated as follows.

[0179] [Solid component concentration]

[0180] 1g of the resin solution obtained in the synthesis example was impregnated in a glass filter [weight: W1(g)] and weighed [W1(g)]. The weight [W2(g)] was calculated based on the weight after heating at 161°C for 2 hours using the following formula.

[0181] Solid component concentration (wt%) = 111 × (W2 - W1) / (W1 - W1)

[0182] [Epoxy Equivalent]

[0183] The resin solution was dissolved in dioxane, and then a tetraethylammonium bromide acetic acid solution was added. The solution was titrated using a potentiometric titration apparatus "COM-1611" (manufactured by Hiranuma Sangyo Co., Ltd.) and a 1 / 11N-perchloric acid solution.

[0184] [Acid Value]

[0185] The resin solution was dissolved in dioxane, and the solution was determined by titration with a 1 / 11 N-KOH aqueous solution using a potentiometric titration apparatus "COM-1611" (manufactured by Hiranuma Sangyo Co., Ltd.).

[0186] [Molecular weight]

[0187] The weight-average molecular weight (Mw) was determined using gel permeation chromatography (GPC) with a configuration of "HLC-8221GPC" (manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuper H-2111 (2 columns) + TSKgelSuper H-3111 (1 column) + TSKgelSuper H-1111 (1 column) + TSKgelSuper H-5111 (1 column) (manufactured by Tosoh Corporation), temperature: 11℃, speed: 1.6 ml / min). The Mw was calculated by converting the Mw values ​​to those of standard polystyrene (manufactured by Tosoh Corporation, PS-oligomer kit).

[0188] [Molar absorptivity]

[0189] The molar absorptivity of the acyl oxime photopolymerization initiator was determined using a UV-Vis-NIR spectrophotometer “UH1151” (manufactured by Hitachi High Technology Co., Ltd.).

[0190] [Average Particle Diameter]

[0191] The average particle size of the silica particles was determined using a particle size analyzer, the FPAR-1111 (manufactured by Otsuka Electronics Co., Ltd.), employing a dynamic light scattering method and a cumulative method.

[0192] In addition, the abbreviations used in the synthetic examples and comparative examples are as follows.

[0193] DCPMA: Dicyclopentyl methacrylate

[0194] GMA: Glycidyl methacrylate

[0195] St: Styrene

[0196] AA: Acrylic acid

[0197] SA: Succinic anhydride

[0198] BPFE: Bisphenol fluorene type epoxy compound (the reaction product of 9,9-bis(1-hydroxyphenyl)fluorene and chloromethyloxetine)

[0199] BPDA: 3,3',1,1'-Biphenyltetracarboxylic dianhydride

[0200] THPA: Tetrahydrophthalic anhydride

[0201] AIBN: Azobisisobutyronitrile

[0202] TDMAMP: Tris-dimethylaminomethylphenol

[0203] HQ: Hydroquinone

[0204] TEA: Triethylamine

[0205] TEAB: Tetraethylammonium bromide

[0206] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0207] [Synthesis example 1]

[0208] PGMEA (311 g) was placed in a 1 L four-necked flask equipped with a reflux condenser. After purging the flask system with nitrogen, the temperature was raised to 121 °C. In the flask, a monomer mixture (a mixture of AIBN (11 g) dissolved in DCPMA (77.1 g, 1.35 mol), GMA (19.8 g, 1.35 mol), and St (31.2 g, 1.31 mol)) was added dropwise over a period of 2 hours using a dropping funnel. The mixture was then stirred at 121 °C for 2 hours to obtain a copolymer solution.

[0209] Subsequently, after purging the flask system with air, AA (21.1 g, 95% of glycidyl groups), TDMAMP (1.8 g), and HQ (1.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 121 °C for 6 hours to obtain a copolymer solution containing polymerizable unsaturated groups. SA (31.1 g, 91% of the molar amount of AA) and TEA (1.5 g) were added to the obtained copolymer solution containing polymerizable unsaturated groups, and the mixture was reacted at 121 °C for 1 hour to obtain an alkali-soluble copolymer resin solution (A)-1 containing polymerizable unsaturated groups. The solids concentration of the resin solution was 16.1% by mass, the acid value (converted from solids content) was 76 mg KOH / g, and the Mw analyzed by GPC was 5311.

[0210] [Synthesis example 2]

[0211] BPFE (111.1 g, 1.23 mol), AA (33.2 g, 1.16 mol), PGMEA (157.1 g), and TEAB (1.18 g) were added to a 511 ml four-necked flask equipped with a reflux condenser, and the mixture was stirred at 111 °C–115 °C for 21 hours to carry out the reaction. Subsequently, BPDA (35.3 g, 1.12 mol) and THPA (18.3 g, 1.12 mol) were added to the flask, and the mixture was stirred at 121 °C–125 °C for 6 hours to obtain a alkali-soluble resin (A)-2 containing polymerizable unsaturated groups. The obtained resin solution had a solids content of 56.1% by mass, an acid value (converted from solids content) of 113 mg KOH / g, and a Mw of 3611 as determined by GPC analysis.

[0212] The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 36 were prepared by mixing the formulations according to the proportions shown in Tables 1 to 7. All values ​​in Tables 1 to 7 represent parts by mass. In Tables 1 to 7, alkali-soluble resins containing polymerizable unsaturated groups are listed as resins.

[0213] (Alkali-soluble resins containing polymerizable unsaturated groups)

[0214] (A)-1: The resin solution obtained in Synthesis Example 1 (solid content concentration 16.1% by mass)

[0215] (A)-2: The resin solution obtained in Synthesis Example 2 (solid content concentration 56.1% by mass)

[0216] (Photopolymerizable monomers)

[0217] (B): A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA (acrylate equivalent 96-115), manufactured by Nippon Kayaku Co., Ltd.)

[0218] (Epoxy compounds)

[0219] (C)-1: 3',1'-Epoxycyclohexylmethyl 3',1'-Epoxycyclohexanecarboxylate (Epoxy equivalent 131, manufactured by Daicel Inc.)

[0220] (C)-2: Butanetetracarboxylic acid tetra(3,1-epoxycyclohexylmethyl) modified ε-caprolactone (epoxy equivalent 197, manufactured by Daicel Inc.)

[0221] (C)-3: HiREM-1 (epoxy equivalent 113, manufactured by Shikoku Chemical Industry Co., Ltd.)

[0222] (C)-1: 1,2-Epoxy-1-(2-oxetanepropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE 3151, epoxy equivalent 181, manufactured by Daicel Inc.)

[0223] (C)-5: Triphenylmethane type epoxy resin (EPPN-511H, epoxy equivalent 161, manufactured by Nippon Kayaku Co., Ltd.)

[0224] (Photopolymerization initiator)

[0225] (D)-1: Oxime ester photopolymerization initiator (Adeka arkls NCI-831, manufactured by ADEKA Inc., "Adeka arkls" is a registered trademark of this company)

[0226] (D)-2: Pentaerythritol tetra(3-mercaptopropionate)

[0227] (solvent)

[0228] (E)-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0229] (E)-2: Diethylene glycol ethyl methyl ether (EDM)

[0230] (Curing agents and curing accelerators)

[0231] (F)-1: Trimeric tricarboxylic anhydride

[0232] (F)-2: A PGMEA solution containing 2.1% by mass of 1,8-diazabicyclo[5.1.1]undec-7-ene (DBU(R), manufactured by San-apro Inc.)

[0233] (Coloring material)

[0234] (G)-1: A pigment dispersion of resin-coated carbon black (25% by mass), polymeric dispersant (5% by mass), and PGMEA solvent (31.1% by mass) (solids concentration).

[0235] (G)-2: A pigment dispersion (solids concentration 35.1% by mass) consisting of 25.1% titanium black, 2.1% polymeric dispersant, 8.1% dispersion resin (alkali-soluble resin (A)-2) of Synthesis Example 2) in PGMEA solvent.

[0236] (Silicon dioxide particles)

[0237] (H)-1: Silica PGMEA dispersion "YA111C" (manufactured by Admatechs Inc., solid content concentration 21% by mass, average particle size 11 nm)

[0238] (H)-2: Silica PGMEA dispersion "YA151C" (manufactured by Admatechs Inc., solid content concentration 11% by mass, average particle size 51nm)

[0239] (H)-3: Silica PGMEA dispersion "YC111C" (manufactured by Admatechs Inc., solid content concentration 51% by mass, average particle size 111 nm)

[0240] (H)-1: Hollow silica isopropanol dispersion (manufactured by Nichih Catalyst Chemical Co., Ltd., solid content concentration 21% by mass, average particle size 75nm, porosity 16% by volume).

[0241] (surfactant)

[0242] (I): Megafac F-175 (manufactured by DIC Corporation, "Megafac" is a registered trademark of this company)

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250] [evaluate]

[0251] The following evaluation was conducted using the cured films (coatings) obtained by curing the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 36. The evaluation results are shown in Tables 8 to 13.

[0252] (Preparation of hardened film (coating) for evaluating development properties)

[0253] Using a spin coater, the photosensitive resin compositions shown in Tables 1 to 7 were coated onto surfaces pre-irradiated with a wavelength of 251 nm and an illuminance of 1111 mJ / cm² using a heat-cured film thickness of 1.2 μm. 2 A 125mm × 125mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate"), whose surface had been cleaned with ultraviolet light, was pre-baked at 85°C for 1 minute using a hot plate to create a hardened film (coating). Subsequently, the exposure gap was adjusted to 111μm, and a negative photomask with a line / space ratio of 11μm / 51μm was applied to the hardened film (coating), using i-ray irradiation of 31mW / cm². 2 Irradiation by an ultra-high pressure mercury lamp: 81 mJ / cm 2 Ultraviolet light is used to perform a photocuring reaction on the photosensitive parts.

[0254] Subsequently, the hardened film (coating) after exposure was subjected to a 1.11% potassium hydroxide solution at 25°C at a concentration of 1 kgf / cm². 2 The spray pressure was used for development treatments of 11 seconds and 21 seconds, starting from the development time (break time = BT) from the start of pattern appearance. Afterwards, a 5 kgf / cm² spray was applied. 2 The unexposed portions of the hardened film (coating) were removed by spraying water to form a hardened film pattern on the glass substrate. The substrate was then formally hardened (post-baked) at 85°C for 61 minutes using a hot air dryer to obtain substrates with hardened films as described in Examples 1 to 13 and Comparative Examples 1 to 36.

[0255] [Evaluation of developing properties]

[0256] (Pattern line width)

[0257] (Evaluation Method)

[0258] For the pattern linewidth after formal curing (post-baking), the pattern linewidth with a mask width of 11 μm was measured using a length measuring microscope "XD-21" (manufactured by Nikon Corporation). Furthermore, the pattern linewidth was evaluated under both BT+11 sec and BT+21 sec conditions.

[0259] (Evaluation Criteria)

[0260] ○: Within a pattern linewidth range of 11±2μm

[0261] ×: Outside the range where the pattern line width is 11±2μm

[0262] (Linearity of the pattern)

[0263] (Evaluation Method)

[0264] The 11 μm mask pattern after formal curing (post-baking) was observed using an optical microscope. Furthermore, the linearity of the pattern was evaluated under both BT+11 seconds and BT+21 seconds conditions. A value above △ was considered acceptable.

[0265] (Evaluation Criteria)

[0266] ○: It has not been confirmed that the edges of the pattern have become jagged.

[0267] △: Locally confirmed that the edges of the pattern become jagged.

[0268] ×: The pattern is distributed throughout, but the edges become jagged.

[0269] (Pattern fit)

[0270] (Evaluation Method)

[0271] The 11 μm mask pattern after formal curing (post-baking) was observed using an optical microscope. Furthermore, the pattern adhesion was evaluated under development conditions of BT+21 seconds, with a value above △ considered acceptable.

[0272] (Evaluation Criteria)

[0273] ○: No peeling was observed in the pattern.

[0274] △: Delamination was observed only in a portion of the pattern.

[0275] ×: Most of the pattern has peeled off.

[0276] (Preparation of hardened films (coatings) for evaluating optical density (OD))

[0277] Using a spin coater, the photosensitive resin compositions shown in Tables 1 to 7 were coated onto surfaces pre-irradiated with a wavelength of 251 nm and an illuminance of 1111 mJ / cm² using a heat-cured film thickness of 1.2 μm. 2A 125mm × 125mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate"), whose surface had been cleaned with ultraviolet light, was pre-baked at 85°C for 1 minute using a hot plate to create a hardened film (coating). Subsequently, the exposure gap was adjusted to 111μm, and a negative photomask with a line / space ratio of 11μm / 51μm was applied to the hardened film (coating), using i-ray irradiation of 31mW / cm². 2 Irradiation by an ultra-high pressure mercury lamp: 81 mJ / cm 2 Ultraviolet light is used to carry out a photocuring reaction.

[0278] Subsequently, the hardened film (coating) after exposure was subjected to a 1.11% potassium hydroxide solution at 25°C at a concentration of 1 kgf / cm². 2 A development process of 21 seconds is performed, starting from the time the pattern begins to appear (interval = BT), followed by a development process at a spray pressure of 5 kgf / cm². 2 The unexposed portions of the hardened film (coating) were removed by spraying water to form a hardened film pattern on the glass substrate. The substrate was then formally hardened (post-baked) at 85°C for 61 minutes using a hot air dryer to obtain substrates with hardened films as described in Examples 9 to 13 and Comparative Examples 9 to 36.

[0279] [Optical Density Evaluation]

[0280] (Evaluation Method)

[0281] The optical density (OD) of the fabricated hardened film (coating) was evaluated using a Macbeth via a density meter. Additionally, the thickness of the hardened film (coating) formed on the substrate was measured, and the optical density (OD) value divided by the film thickness was set as OD / μm.

[0282] Optical density (OD) is calculated using the following formula (1).

[0283] Optical density (OD) = -log 11 T (1)

[0284] (T represents transmittance)

[0285] [Soluble Resistance Evaluation]

[0286] (Evaluation Method)

[0287] The surface of a hardened film (coating) prepared in the same manner as for optical density (OD) evaluation is continuously rubbed 21 times using cotton fibers impregnated in PGMEA. Furthermore, a value of △ or higher is considered acceptable.

[0288] (Evaluation Criteria)

[0289] ○: No dissolution or damage was observed on the surface of the hardened film (coating).

[0290] △: Dissolution was observed on only a portion of the surface of the hardened film (coating), and only a portion was also damaged.

[0291] ×: The surface of the hardened film (coating) has softened, and most of it is damaged.

[0292] (Preparation of hardened film (coating) for reflectivity evaluation)

[0293] Using a spin coater, the photosensitive resin compositions shown in Tables 1 to 7 were coated onto surfaces pre-irradiated with a wavelength of 251 nm and an illuminance of 1111 mJ / cm² using a heat-cured film thickness of 1.2 μm. 2 A 125mm × 125mm glass substrate "#1737" (manufactured by Corning) (hereinafter referred to as "glass substrate") with a surface cleaned by ultraviolet light was pre-baked at 85°C for 1 minute using a heating plate to create a hardening film (coating). Subsequently, it was formally hardened (post-baked) at 85°C for 61 minutes using a hot air dryer to obtain the substrates with hardened films of Examples 9 to 13 and Comparative Examples 9 to 36.

[0294] [Reflectivity Evaluation]

[0295] (Evaluation Method)

[0296] For the substrate with the hardened film (coating) that was fabricated, the reflectance of the hardened film (coating) side was measured using a UV-Vis-IR spectrophotometer "UH1151" (manufactured by Hitachi High-Tech Science Co., Ltd.) at an incident angle of 2°.

[0297]

[0298]

[0299]

[0300] According to the evaluation results of Examples 25 to 32, by making the content of the coloring material as component (G) 21% to 81% by mass relative to the solid content in the photosensitive resin composition, sufficient light-blocking properties can be obtained, and the desired development characteristics (pattern line width, pattern straightness) can be obtained. This is believed to be because the original content of the photosensitive resin as a binder is sufficient to make the development characteristics, especially the pattern straightness, appropriate.

[0301] Based on the evaluation results of Examples 1-13 and Comparative Examples 1-36, it can be seen that if the mass of component (C) in the solid composition is in the range of 5% to 17% by mass, a hardened film (coating) that satisfies solvent resistance and has excellent pattern adhesion can be obtained. On the other hand, it can be seen that if the mass of component (C) is less than 1% by mass of the total solid composition, the solvent resistance of the hardened film (coating) is insufficient; if it is 17% by mass or more, although the solvent resistance of the hardened film (coating) is satisfied, the pattern adhesion is reduced, and pattern peeling during development becomes significant.

[0302] According to the results of Comparative Examples 33 to 36, by using an epoxy compound having an epoxy cyclohexyl group as component (C), a hardened film (coating) with excellent solvent resistance can be obtained compared with a system using an epoxy compound having a glycidyl group.

[0303] It is evident that the cured films (coatings) of Examples 1 to 13, which contain (C)-1 to (C)-3 having an epoxy cyclohexyl group as component (C), generally exhibit excellent solvent resistance. Specifically, it is found that using (C)-2, which has one epoxy cyclohexyl group within its molecule, as component (C) effectively improves the solvent resistance of the cured film (coating).

[0304] Based on the results of Examples 39 to 13, it is evident that adding (H) silica particles can reduce the reflectivity measured on the self-coated film surface. This is believed to be because, in particular, using solid / hollow silica particles with an average particle size of 1 nm to 95 nm reduces the unevenness of the hardened film (coating) surface, thus suppressing deviations in reflectivity within the hardened film (coating) surface.

[0305] [Industrial Applicability]

[0306] Even if the process of forming the hardened film pattern does not include a heat curing step at a temperature exceeding 111°C, the photosensitive resin composition of the present invention can form a hardened film pattern with a linewidth in the range of 11±2 μm, excellent development adhesion, linearity, and good solvent resistance. Therefore, for resin films made of PET, PEN, etc., with a heat resistance temperature of 111°C or below, and for substrates with organic devices such as organic EL or organic TFT on glass substrates or silicon wafers, hardened film patterns possessing the aforementioned characteristics can be formed. The photosensitive resin composition of the present invention is suitable for setting hardened films such as transparent film patterns, insulating film patterns, black matrices, and isolation wall patterns required for forming color filters, organic EL pixels, or touch screens on substrates with low heat resistance temperatures, thereby enabling the substrate with the hardened film to be used in the manufacture of display devices such as liquid crystals or organic ELs, as well as in the manufacture of solid-state photographic elements such as complementary metal-oxide-semiconductors (CMOS) and touch screens.

Claims

1. A photosensitive resin composition for forming a hardened film on a substrate having a heat resistance temperature of 140°C or lower, the photosensitive resin composition comprising the following components: (A) Component: an alkali-soluble resin containing an unsaturated group; (B) Component: a photopolymerizable monomer having two or more ethylenic unsaturated bonds; (C) Component: an epoxy compound having two or more 3,4-epoxycyclohexyl groups; (D) Component: a photopolymerization initiator; (E) Component: a solvent; (G) Component: a coloring material selected from the group consisting of an organic pigment or an inorganic pigment; and (H) Component: a silica particle, and the average particle diameter of the silica particle is 1 nm to 95 nm, the content of the (C) Component is 5 mass% to 17 mass% with respect to the total mass of the solid components, the content of the (G) Component is 0 mass% to 40 mass% with respect to the total mass of the solid components, the alkali-soluble resin containing an unsaturated group of the (A) Component is an alkali-soluble resin containing an unsaturated group represented by General Formula (3), one or more of Z in General Formula (3) is a substituent represented by General Formula (4), and n is an integer of 1 to 20, in General Formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2, the (C) Component is an epoxy compound represented by General Formula (1) or General Formula (2), in General Formula (1), X is a single bond or a divalent organic group having a carbon number of 1 to 20 which can internally include a hetero atom, and in General Formula (2), a, b, c, and d are each independently 0 or 1, and a + b + c + d = 1 to 3.

3. The photosensitive resin composition according to claim 1, comprising (F) Component: a hardener and / or a hardening accelerator for an epoxy compound, and the total amount of the (C) Component and the (F) Component is 6 mass% to 24 mass% with respect to the total mass of the solid components. The (F) Component contains an acid anhydride. The (G) Component 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. The (D) Component is an acyl oxime-based photopolymerization initiator having a molar absorption coefficient of 10,000 L / mol-cm or more at 365 nm. The (D) Component is an acyl oxime-based photopolymerization initiator represented by General Formula (5), R6, R7, and R8 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, and R8 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 can be substituted with a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 alkanoyl group, a halogen, the alkylene moiety can include an unsaturated bond, an ether bond, a thioether bond, an ester bond, and the alkyl group can be any one of a straight chain, a branch, or a ring.

8. A hardened film obtained by hardening the photosensitive resin composition according to any one of claims 1 to 7.

9. A substrate with a hardened film having the hardened film according to claim 8. ​ ​ ​ ​ In formula (3), R1, R2, R3, and R4 are each independently a hydrogen atom, an alkyl group having a carbon number of 1 to 5, 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-, fluorene-9,9-diyl, 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); wherein, ​ ​ 2. The photosensitive resin composition according to claim 1, wherein ​ ​ ​ ​ 4. The photosensitive resin composition according to claim 3, wherein ​ 5. The photosensitive resin composition according to claim 1, wherein ​ 6. The photosensitive resin composition according to claim 1, wherein ​ 7. The photosensitive resin composition according to claim 6, wherein ​ ​ ​ ​ 10. A method for manufacturing a substrate with a hardened film, which is a method for manufacturing a substrate with a hardened film by forming a hardened film pattern on a substrate having a heat resistance temperature of 140°C or lower, wherein The photosensitive resin composition according to any one of claims 1 to 7 is coated on a substrate, and exposed through a photomask, and the unexposed portion is removed by development, and a hardened film pattern is formed by heating at 140°C or lower.

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