TWI877523B - Photosensitive resin composition and method of producing the substrate having the resin film thereof - Google Patents

Abstract

The present invention provides a method for producing a substrate with a resin film by low-temperature curing a photosensitive resin composition which is suitable for forming a resin film pattern on a plastic substrate having a heat resistance of up to 140°C and can obtain a resin film pattern having excellent solvent resistance on the substrate. A photosensitive resin composition comprising: (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two ethylenically unsaturated bonds, (C) an epoxy compound, (D) a hardener and/or a hardening accelerator for the epoxy compound, (E) a photopolymerization initiator, and (F) a solvent, wherein the total amount of the component (C) and the component (D) in the solid component excluding the component (F) is 6% by mass to 24% by mass.

Description

Photosensitive resin composition and method for producing substrate with resin film

The present invention relates to a photosensitive resin composition of a specific composition for forming a resin film pattern on a substrate with a heat-resistant temperature of 140°C or less (a plastic substrate, a substrate with an organic device such as an organic electroluminescence (EL) or an organic thin film transistor (TFT) on a glass substrate or a silicon wafer, etc.) by photolithography, and also to a method for manufacturing a substrate with a resin film.

Recently, for the purpose of making devices flexible or one-chip, there is a demand for, for example, directly forming a resin film (transparent insulating film, etc.) pattern, a coloring film pattern, or a light-shielding film pattern on a plastic substrate (plastic film, resin film) such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or directly forming a resin film pattern, a coloring film pattern, or a light-shielding film pattern on a substrate having an organic device such as an organic EL or an organic TFT on a glass substrate or a silicon wafer. However, the actual situation is that the heat resistance temperature of the plastic substrate itself is usually only about 140°C at most, and in the case of a substrate with an organic device, it is 120°C at most, and the heat resistance in the actual manufacturing process is preferably below 100°C. Therefore, when a resin film pattern, a coloring film pattern, or a light-shielding film pattern is formed on a plastic substrate or a device, there is a problem that the film strength of the pattern formed at a thermal calcination temperature below 140°C is insufficient, and in the subsequent steps (for example, in the case of a light-shielding film pattern, the solvent resistance when applying each RGB anti-etching agent or the alkali resistance during alkali development, etc.), the film reduction, surface roughness, pattern peeling, and other undesirable conditions will occur. Moreover, at a hot calcination temperature below 120°C, it is extremely difficult to form a resin film pattern, a coloring film pattern, or a light-shielding film pattern with the required film strength.

Therefore, for example, Japanese Patent Publication No. 2003-15288 (Patent Document 1) discloses that a substrate is formed by using an alkali-soluble resin of an acrylic copolymer as a base and containing a thermal polymerization initiator in addition to a photopolymerization initiator, applying the composition to a plastic substrate, exposing, patterning, and calcining at 150°C. Although the residue and adhesion to the substrate (peeling test) are ensured, there is no description of pattern line width, development margin, and reliability (solvent resistance, alkali resistance), which are still insufficient. Japanese Patent Publication No. 2017-181976 (Patent Document 2) discloses a photosensitive resin composition for a light-shielding film, which comprises: an alkali-soluble resin containing an unsaturated group, a photopolymerizable monomer having at least three ethylenic unsaturated bonds, an oxime ester polymerization initiator, an azo polymerization initiator, and a light-shielding component. However, in the case of forming a resin film pattern on a plastic substrate with low heat resistance or a substrate with an organic device at a low temperature, it is still insufficient, and a photosensitive resin composition is required that can form a resin film pattern with better development adhesion or linearity, and excellent solvent resistance or alkali resistance. [Prior Art Document]

[Patent document] [Patent document 1] Japanese Patent Publication No. 2003-15288 [Patent document 2] Japanese Patent Publication No. 2017-181976

[Problem to be solved by the invention] The present invention is made in view of the above-mentioned problem, and its purpose is to provide a photosensitive resin composition suitable for forming a resin film (transparent insulating film, etc.) pattern, a coloring film pattern, a light-shielding film pattern on a plastic substrate or a substrate with an organic device having a heat resistance of up to 140°C, and when applied to such plastic substrates or substrates with an organic device having low heat resistance, a resin film pattern, a coloring film pattern, a light-shielding film pattern, etc. with excellent solvent resistance or alkali resistance is obtained, and a method for manufacturing the obtained substrate with a resin film. These resin film patterns, coloring film patterns, light-shielding film patterns, etc. can be used as components of various displays, touch screen sensors, image sensors, etc. [Technical means to solve the problem]

Therefore, the inventors of the present invention have made great efforts to study a method for forming patterns using a specific photosensitive resin composition that can obtain good development adhesion or pattern linearity through thermal curing at a temperature below 140°C and can obtain excellent solvent resistance or alkali resistance, such as resin film patterns, colored film patterns, light-shielding film patterns, etc. As a result, they found that: in a composition comprising an alkali-soluble resin containing a specified polymerizable unsaturated group, a photopolymerizable monomer, an epoxy compound, a hardener and/or a hardening accelerator for an epoxy compound, and a photopolymerization initiator, by using a composition containing an epoxy compound and a hardener and/or a hardening accelerator for an epoxy compound within a specific range, the above-mentioned problem can be solved, thereby completing the present invention.

The present invention is a photosensitive resin composition, which is used to coat the photosensitive resin composition on a substrate having a heat-resistant temperature of 140°C or less, expose the substrate through a photoresist, remove the unexposed portion by development, and then heat the substrate at a temperature of 140°C or less to form a predetermined resin film pattern, thereby manufacturing a substrate with a resin film. The photosensitive resin composition is characterized in that it contains: (A) an alkali-soluble resin containing an unsaturated group, (B) a photopolymerizable monomer having at least two ethylenic unsaturated bonds, (C) an epoxy compound, (D) a hardener and/or a hardening accelerator for the epoxy compound, (E) a photopolymerization initiator, and (F) a solvent, and The total amount of components C and D in the solid components excluding component F is 6% to 24% by mass.

The photosensitive resin composition of the present invention may further include (G) a colorant containing an organic pigment or an inorganic pigment. The colorant of component G is preferably a light-shielding material containing an organic black pigment or an inorganic black pigment. The epoxy equivalent of the epoxy compound of component C is preferably 100 g/eq to 300 g/eq. The curing agent and/or curing accelerator of component D is preferably an acid anhydride. As the photopolymerization initiator of component E, it is preferred to use an acyl oxime-based photopolymerization initiator having a molar absorption coefficient of 10,000 or more at 365 nm. The photopolymerization initiator of component E is preferably an acyl oxime-based photopolymerization initiator of general formula (1). [Chemistry 1] ^R1 and ^R2 independently represent C1-C15 alkyl, C6-C18 aryl, C7-C20 arylalkyl or C4-C12 heterocyclic group, and ^R3 represents C1-C15 alkyl, C6-C18 aryl or C7-C20 arylalkyl. Here, the alkyl and aryl groups may be substituted by C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkanoyl or halogen, and the alkylene part may contain unsaturated bonds, ether bonds, thioether bonds or ester bonds. In addition, the alkyl group may be any of linear, branched or cyclic alkyl groups. The unsaturated group-containing alkali-soluble resin of component A is preferably an unsaturated group-containing alkali-soluble resin represented by general formula (2). [Chemistry 2] (wherein, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ⁸ represents a hydrogen atom or a methyl group, A represents -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, fluorene-9,9-diyl or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ each independently represent a hydrogen atom or -OC-Z-(COOH) _m (wherein, Z represents a divalent or trivalent carboxylic acid residue, m represents a number of 1 or 2), and n represents an integer of 1 to 20)

Another aspect of the present invention is a method for manufacturing a substrate with a resin film, which is a method for manufacturing a substrate with a resin film by forming a resin film pattern on a substrate having a heat-resistant temperature of 140°C or less, and is characterized in that: the photosensitive resin composition according to technical solution 1 is used as a photosensitive resin composition for forming a resin film pattern, and the photosensitive resin composition is applied to the substrate and exposed through a photoresist, and the unexposed part is removed by development, and then heated at a temperature below 140°C to form a prescribed resin film pattern. [Effect of the invention]

The photosensitive resin composition of the present invention can form a resin film pattern with a resolution of 5 μm to 50 μm in line width even if the process of manufacturing the resin film pattern does not include a step of heat curing at a temperature exceeding 140°C, thereby forming a resin film pattern with excellent developability and linearity and good solvent resistance or alkali resistance. Therefore, a desired resin film pattern can be formed on a resin film such as PET, PEN, etc. having a heat-resistant temperature of 140°C or less, and a substrate with an organic device such as an organic EL or organic TFT formed on a glass substrate or a silicon wafer (including a substrate in which a protective film is formed and a protective film is laminated after the organic device is formed).

The present invention is described in detail below. The present invention relates to a photosensitive resin composition for forming a resin film pattern on a substrate having a heat-resistant temperature of 140°C or less, and is a method for manufacturing a low heat-resistant substrate with a resin film in which a resin film pattern is formed by applying a photoprocessing technique such as a photodevelopment method. Since the photosensitive resin composition used has characteristics, the components of the sensory resin composition and their composition ratios are first described.

The alkali-soluble resin containing a polymerizable unsaturated group as the component (A) in the photosensitive resin composition can be used without particular limitation as long as it has a polymerizable unsaturated group and an acidic group in the molecule. Representative examples of the polymerizable unsaturated group are an acrylic group or a methacrylic group, and representative examples of the acidic group are a carboxyl group.

The preferred weight average molecular weight (Mw) and acid value range of the alkali-soluble resin containing a polymerizable unsaturated group vary depending on the resin skeleton, but generally, the Mw is 2000 to 50000 and the acid value is 60 mgKOH/g to 120 mgKOH/g. If the Mw is less than 2000, there is a concern that the adhesion of the pattern during alkali development may be reduced, and if the Mw exceeds 50000, there is a concern that the photosensitive resin composition may not have a suitable development time due to a significantly reduced developability. If the acid value is less than 60, residues are likely to remain during alkaline development, and if the acid value is greater than 120, the alkaline developer penetrates too quickly, which is not a preferred dissolution development and may cause peeling development, so both are not preferable. The unsaturated group-containing alkali-soluble resin of component (A) may be used alone or as a mixture of two or more.

The first example of the unsaturated group-containing alkali-soluble resin as the component (A) that is preferably used is an epoxy (meth)acrylate acid adduct obtained by reacting a compound having two or more epoxy groups with (meth)acrylic acid (hereinafter referred to as "acrylic acid and/or methacrylic acid"), and reacting (a) a monoanhydride of a dicarboxylic acid or a tricarboxylic acid and/or (b) a tetracarboxylic dianhydride with the obtained epoxy (meth)acrylate compound having a hydroxyl group. Examples of the compound having two or more epoxy groups that is derived into the epoxy (meth)acrylate acid adduct include bisphenol-type epoxy compounds and novolac-type epoxy compounds.

The bisphenol type epoxy compound is an epoxy compound having two glycidyl ether groups obtained by reacting bisphenols with epichlorohydrin. The reaction is usually accompanied by oligomerization of the glycidyl ether compound, and thus includes an epoxy compound having two or more bisphenol skeletons. Examples of the bisphenols used in the reaction include bis(4-hydroxyphenyl)ketone, bis(4-hydroxy-3,5-dimethylphenyl)ketone, bis(4-hydroxy-3,5-dichlorophenyl)ketone, bis(4-hydroxyphenyl)sulfate, bis(4-hydroxy-3,5-dimethylphenyl)sulfate, bis(4-hydroxy-3,5-dichlorophenyl)sulfate, bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxy-3,5-dimethylphenyl)hexafluoropropane, bis(4-hydroxyphenyl)sulfate, -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-dibromophenyl)methane 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3,5-dimethylphenyl)ether, bis(4-hydroxy-3,5-dichlorophenyl)ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9, 9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, 4,4-bisphenol, 3,3-bisphenol, etc. Among them, bisphenols having a fluorene-9,9-diyl group can be particularly preferably used.

As the (a) dicarboxylic acid or tricarboxylic acid monoanhydride to be reacted with epoxy (meth)acrylate, there can be used a monoanhydride of a chain alkyl dicarboxylic acid or tricarboxylic acid, a monoanhydride of alicyclic dicarboxylic acid or tricarboxylic acid, or a monoanhydride of an aromatic dicarboxylic acid or tricarboxylic acid. Here, the monoanhydride of the chain alkyl dicarboxylic acid or tricarboxylic acid includes, for example, monoanhydrides of succinic acid, acetosuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid, and the like, and further, monoanhydrides of dicarboxylic acids or tricarboxylic acids into which any substituents are introduced. In addition, examples of the monoanhydride of alicyclic dicarboxylic acids or tricarboxylic acids include monoanhydrides of cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, and the like, and further monoanhydrides of dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced. Furthermore, examples of the monoanhydride of aromatic dicarboxylic acids or tricarboxylic acids include monoanhydrides of phthalic acid, isophthalic acid, trimellitic acid, and the like, and further monoanhydrides of dicarboxylic acids or tricarboxylic acids into which an arbitrary substituent is introduced.

In addition, as the (b) tetracarboxylic acid dianhydride to be reacted with epoxy (meth)acrylate, the dianhydride of a chain alkane tetracarboxylic acid, the dianhydride of alicyclic tetracarboxylic acid, or the dianhydride of an aromatic tetracarboxylic acid can be used. Here, as the dianhydride of the chain alkane tetracarboxylic acid, there are, for example, dianhydrides of butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, etc., and further, dianhydrides of tetracarboxylic acids into which an arbitrary substituent is introduced. In addition, as the dianhydride of alicyclic tetracarboxylic acid, there are, for example, dianhydrides of cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, etc., and further, dianhydrides of tetracarboxylic acids into which an arbitrary substituent is introduced. Furthermore, examples of the dianhydride of aromatic tetracarboxylic acid include dianhydrides of pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenyl ether tetracarboxylic acid, and the like. Furthermore, dianhydrides of tetracarboxylic acids into which an arbitrary substituent is introduced may be mentioned.

The molar ratio (a)/(b) of the anhydride of (a) dicarboxylic acid or tricarboxylic acid and (b) tetracarboxylic acid dianhydride reacting with epoxy (meth)acrylate may be 0.01 to 10.0, preferably 0.02 or more and less than 3.0. If the molar ratio (a)/(b) deviates from the above range, the optimal molecular weight for preparing a photosensitive resin composition having good photo-patterning properties cannot be obtained, which is not good. Furthermore, there is a tendency that the smaller the molar ratio (a)/(b), the larger the molecular weight and the lower the alkali solubility.

Epoxy (meth)acrylate acid adducts can be produced by a known method, for example, the method described in Japanese Patent Laid-Open No. 8-278629 or Japanese Patent Laid-Open No. 2008-9401. First, as a method for reacting (meth)acrylic acid with an epoxy compound, there is a method in which, for example, an equal mole of (meth)acrylic acid to the epoxy group of the epoxy compound is added to a solvent, and the reaction is carried out by heating and stirring at 90°C to 120°C while blowing air in the presence of a catalyst (triethylbenzylammonium chloride, 2,6-diisobutylphenol, etc.). Next, as a method for reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product, there is a method in which a predetermined amount of an epoxy acrylate compound, an acid dianhydride, and an acid monoanhydride are added to a solvent, and the mixture is heated and stirred at 90° C. to 130° C. in the presence of a catalyst (tetraethylammonium bromide, triphenylphosphine, etc.) to react. The epoxy acrylate acid adduct obtained by the above method has a skeleton of the general formula (2).

Other examples of resins that can be preferably used as the alkali-soluble resin containing a polymerizable unsaturated group as the component (A) include resins having a (meth)acrylic acid group and a carboxyl group in copolymers such as (meth)acrylic acid and (meth)acrylic acid esters. For example, an alkali-soluble resin containing a polymerizable unsaturated group is obtained by copolymerizing (meth)acrylic acid esters including (meth)acrylic acid glycidyl ester in a solvent to obtain a copolymer as a first step, reacting (meth)acrylic acid with the obtained copolymer as a second step, and reacting an anhydride of a dicarboxylic acid or a tricarboxylic acid in a third step. For examples that can also be preferably used in these copolymers, reference can be made to the examples specifically shown in Japanese Patent Application No. 2017-33662.

As another example, a carbamate compound obtained by reacting a polyol compound having an ethylenic unsaturated bond in the molecule as the first component, a diol compound having a carboxyl group in the molecule as the second component, and a diisocyanate compound as the third component can be cited. As a resin of the above system, the resin disclosed in Japanese Patent Laid-Open No. 2017-76071 can be referred to.

Examples of the photopolymerizable monomer having at least two ethylenically unsaturated bonds in (B) 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, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethoxybenzene di ... (Meth)acrylates such as pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxide-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendrimers having (meth)acrylate groups as compounds having ethylenic double bonds can be used. One or two or more of these can be used. In addition, the photopolymerizable monomer having at least two ethylenic unsaturated bonds can play a role in cross-linking the molecules of the contained alkali-soluble resin. In order to play the above function, it is preferred to use a compound having three or more photopolymerizable groups. The acrylic acid group equivalent obtained by dividing the molecular weight of the monomer by the number of (meth)acrylic acid groups in one molecule may be 50 to 300, and more preferably 80 to 200. Component (B) does not have a free carboxyl group.

Regarding the compound having an ethylenic double bond that can be included in the composition as component (B), a dendrimer having a (meth)acrylic group can be exemplified as a dendrimer obtained by adding a polyhydric alkyl compound to a portion of the carbon-carbon double bonds in the (meth)acrylic ester group of a polyfunctional (meth)acrylic ester compound. Specifically, a dendrimer obtained by reacting a (meth)acrylic ester of a polyfunctional (meth)acrylic ester compound of general formula (3) with a polyhydric alkyl compound of general formula (4) can be exemplified. [Chemistry 3] Here, R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents the remaining part of the ester bond in the formula in which one of the k hydroxyl groups of R ¹⁰ (OH) _k is donated, and k and l independently represent integers of 2 to 20, and k ≧ 1. In addition, R ¹¹ is a single bond or a divalent to hexavalent C1 to C6 alkyl group, and m is 2 when R ¹¹ is a single bond, and represents an integer of 2 to 6 when R ¹¹ is a divalent to hexavalent group. Specific examples of the multifunctional (meth)acrylate compound represented by the general formula (3) include (meth)acrylates such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-modified trihydroxymethylpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and caprolactone-modified pentaerythritol tri(meth)acrylate. These compounds may be used alone or in combination of two or more. Specific examples of the polyvalent olefin compound represented by the general formula (4) include trihydroxymethylpropane tri(olefin acetate), trihydroxymethylpropane tri(olefin propionate), pentaerythritol tetra(olefin acetate), pentaerythritol tri(olefin acetate), pentaerythritol tetra(olefin propionate), dipentaerythritol hexa(olefin acetate), dipentaerythritol hexa(olefin propionate), etc. These compounds may be used alone or in combination of two or more.

Examples of the (C) epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (e.g., NC-7000L manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compounds, trisphenol methane type epoxy compounds, tetraphenol type ethane type epoxy compounds, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, copolymers of methacrylic acid and glycidyl methacrylate containing glycidyl (meth)acrylate as a unit (unit) and t), a copolymer of a monomer having a (meth) acrylic group, an alicyclic epoxy compound represented by 3',4'-epoxyepoxyhexylmethyl 3,4-epoxyepoxyhexanecarboxylate, a polyfunctional epoxy compound having a dicyclopentadiene skeleton (for example, HP7200 series manufactured by DIC Corporation), a 1,2-epoxy-4-(2-oxohexopropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (for example, "EHPE3150" manufactured by Daicel Corporation), an epoxidized polybutadiene (for example, "NISSO-PB·JP-100" manufactured by Nippon Soda Co., Ltd.), an epoxy compound having a silicone skeleton, and the like. As these components, compounds having an epoxy equivalent of 100 g/eq to 300 g/eq and a number average molecular weight of 100 to 5000 are preferred. Furthermore, epoxy compounds having three or more epoxy groups in one molecule are more preferably used. In addition, the component (C) may be used alone or in combination of a plurality of compounds.

As the curing agent for the epoxy compound in the component (D), any compound used as a curing agent for epoxy compounds can be used, and examples thereof include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, Lewis acid compounds, etc. In the present invention, polycarboxylic acid compounds can be preferably used. Examples of the polycarboxylic acid compounds include polycarboxylic acids, polycarboxylic acid anhydrides, and thermally decomposable esters of polycarboxylic acids. The so-called polycarboxylic acid refers to a compound having two or more carboxyl groups in one molecule, for example, 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. As the anhydride of the polycarboxylic acid, the anhydride of the compound exemplified above can be listed, which can be an intermolecular anhydride, and the anhydride of the molecule closed ring is usually used. As the thermally decomposable ester of the polycarboxylic acid, the tert-butyl ester, 1-(alkyloxy)ethyl ester, 1-(alkylthio)ethyl ester of the compound exemplified above can be listed (wherein the alkyl group described here represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group can have a branched structure or a ring structure and can be substituted by any substituent), etc. In addition, as the polycarboxylic acid compound, a polymer or copolymer having two or more carboxyl groups can also be used, and the carboxyl group can be an anhydride or a thermally decomposable ester. Examples of such polymers or copolymers include polymers or copolymers containing (meth)acrylic acid as a component, copolymers containing maleic anhydride as a component, compounds obtained by reacting tetracarboxylic dianhydride with diamine or diol to open the anhydride ring, etc. Among these, it is more 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. Regarding the mixing ratio when using a polycarboxylic acid compound as a hardener for an epoxy compound, the carboxyl group of the polycarboxylic acid compound can be mixed in a manner such that 0.5 mol to 1.0 mol, preferably 0.6 mol to 0.95 mol, is used for 1 mol of the epoxy group of the epoxy compound.

As the curing accelerator of the epoxy compound in the component (D), known compounds that are known as curing accelerators, curing catalysts, latent curing agents, etc. of epoxy compounds can be used, for example, tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organic metal compounds, imidazoles, etc., and particularly suitable are 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene or salts thereof. The amount of curing accelerator added is usually 0.05 to 2 parts by mass relative to 100 parts by mass of epoxy compound. The amount of addition can be adjusted depending on the chemical resistance of the resin film pattern after thermal curing.

(E) The photopolymerization initiator may include, for example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminoacetophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone, and p,p-bisdimethylaminobenzophenone; benzoin ethers such as benzil, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 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, ,4,5-triarylbiimidazole and other biimidazole compounds; 2-trichloromethyl-5-phenylvinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxyphenylvinyl)-1,3,4-oxadiazole and other halogenated methylthiazole compounds; 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)-4,6-bis( Halogenated methyl-S-triazine compounds such as 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxyphenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methylthiophenylvinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime), 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxime-O-benzoic acid O-acyl oxime compounds such as esters, 1-(4-methylthiophenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylthiophenyl)butane-1-one oxime-O-acetate; benzyl dimethyl ketal, thioanthrone, 2-chlorothioanthrone, 2,4-diethylthioanthrone, 2-methylthioanthrone, 2-isopropylthioanthrone and other sulfur compounds; 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-butylbenzimidazole, 2-butylbenzoxazole, and 2-butylbenzothiazole; tertiary amines such as triethanolamine and triethylamine, etc. Among them, in particular, when preparing a photosensitive resin composition containing a colorant, it is preferred to use O-acyl oxime compounds (including ketoxime). Among these, when the coloring agent is used at a high pigment concentration or when a light-shielding film pattern is to be formed, it is preferred to use an O-acyl oxime-based photopolymerization initiator having a molar absorption coefficient of 10,000 or more at 365 nm. As a specific compound group, the O-acyl oxime-based photopolymerization initiator of general formula (1) can be cited. In addition, two or more of these photopolymerization initiators can also be used. Furthermore, the photopolymerization initiator described in the present invention is used in the sense of including a sensitizer.

Examples of the (F) solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol and β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; solvents, methyl solvents, ethyl solvents, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, By using, dissolving and mixing these, a uniform solution-like composition can be prepared, and the solution viscosity can be prepared and used.

As the colorant (G), known organic pigments, inorganic pigments, carbon black, titanium black, etc. can be used without particular limitation. In the case of organic pigments, micronized pigments (pigments having a specific surface area of 50 ^m2 /g or more by the Brunauer-Emmett-Teller (BET) method) are particularly preferred in order to achieve microdispersion with an average particle size of 50 nm or less. Specific examples include azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolone pigments, isoindoline pigments, dioxazine pigments, threne pigments, perylene pigments, perinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, and thioindigo pigments.

As the light-shielding material such as organic black pigment and inorganic black pigment used in the light-shielding film application in the coloring agent (G), black organic pigment, mixed color organic pigment or inorganic pigment can be used without particular limitation. As black organic pigment, for example, perylene black, cyanine black, aniline black, lactamide black, etc. can be listed. As mixed color organic pigment, at least two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, etc. are mixed and the pigment is pseudo-black. As inorganic pigment, carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride, etc. can be listed. These light-shielding materials may be used alone or in combination of two or more. Carbon black is particularly preferred in terms of light-shielding properties, surface smoothness, dispersion stability, and affinity with resins.

The photosensitive resin composition of the present invention may contain additives such as a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, a defoaming agent, a coupling agent, and a surfactant as needed. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylpyrogallol, and phenothiazine. Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of fillers include glass fiber, silicon dioxide, mica, and aluminum oxide. Examples of leveling agents or defoaming agents include silicone, fluorine, and acrylic compounds. In addition, examples of the silane coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like, and examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and the like.

Regarding the preferred composition ratio of each component (A) to (E) and (G) in the solid component (the solid component includes monomer components that become solid components after curing) of the photosensitive resin composition of the present invention, the total amount of the component (C) and the component (D) is preferably 6 mass% to 24 mass%, and particularly preferably 10 mass% to 20 mass%. In addition, the component (B) is 10 mass parts to 60 mass parts, 10 mass parts to 80 mass parts, with respect to 100 mass parts of the component (A), and the component (E) is 2 mass parts to 40 mass parts with respect to 100 mass parts of the total amount of the components (A) and (B). More preferably, the amount of component (B) is 30 to 50 parts by mass per 100 parts by mass of component (A), and the amount of component (E) is 3 to 30 parts by mass per 100 parts by mass of the total amount of components (A) and (B). When a coloring agent is used, the content of component (G) in the solid content is preferably in the range of 20% to 60% by mass.

The colorant of component (G) can be prepared as a colorant dispersion by pre-dispersing it in a solvent together with a dispersant, and then preparing it as a photosensitive resin composition for a colored film. Here, the solvent for dispersion can be the above-mentioned solvent, for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. can be used appropriately. As the dispersant used, known dispersants such as various polymer dispersants can be used. As specific examples of dispersants, known compounds used in existing pigment dispersions (compounds commercially available under the names of dispersants, dispersing wetting agents, dispersion accelerators, etc.) can be used without particular limitation, for example, cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative type dispersants (dispersing aids), etc. In particular, in terms of adsorption to pigments, cationic polymer dispersants having cationic functional groups such as imidazole, pyrrolyl, pyridyl, primary amino, diamino or tertiary amino groups, an amine value of 1 mgKOH/g to 100 mgKOH/g, and a number average molecular weight of 1,000 to 100,000 are suitable. The amount of the dispersant to be added may be 1% to 30% by weight, preferably 2% to 25% by weight, relative to the colorant.

Furthermore, when preparing the colorant dispersion, a part of the alkali-soluble resin containing a polymerizable unsaturated group of the component (A) is co-dispersed in addition to the above-mentioned dispersant, so that when preparing the photosensitive resin composition for the coloring film, it is easy to maintain the exposure sensitivity at a high sensitivity, the adhesion during development is good, and the problem of residue is not easy to be produced. The amount of the component (A) in the colorant dispersion is preferably 2 mass% to 20 mass%, and more preferably 5 mass% to 15 mass%. If the component (A) is less than 2 mass%, the effects of co-dispersion such as increased sensitivity, improved adhesion, and reduced residue cannot be obtained. If it exceeds 20% by mass, the viscosity of the colorant dispersion is high, making it difficult to disperse evenly or taking a lot of time, especially when the colorant content is large. The obtained colorant dispersion is mixed with components (A) to (F) and other components are added as needed to adjust the viscosity to a suitable film-forming condition, thereby preparing the photosensitive resin composition used in the production method of the present invention.

The photosensitive resin composition of the present invention contains the above-mentioned components (A) to (E) and/or (G) as main components. It is desirable that the total amount of components (A) to (E) and/or (G) is 80% by mass, preferably 90% by mass or more, in the solid components (including monomer components that become solid components after curing) excluding the solvent. The amount of the solvent varies depending on the target viscosity and can be contained in the photosensitive resin composition in the range of 60% by mass to 90% by mass.

The method for forming the resin film pattern in the present invention is a common photodevelopment method, which is described in detail below. The method is as follows: first, a photosensitive resin composition is applied to a plastic substrate or a substrate with an organic device, and then the solvent is dried (pre-baked), and then the obtained coating is irradiated with ultraviolet rays through a photoresist to cure the exposed part, and then an alkaline aqueous solution is used to perform development to dissolve the unexposed part to form a pattern, and then post-baking (heat calcination) is performed as post-hardening.

As the substrate used in the manufacturing method of the present invention, i.e., the substrate coated with the photosensitive resin composition composed of a specific composition, a resin film (plastic substrate) such as PET and PEN having a heat-resistant temperature of 140°C or less can be cited. Here, the so-called heat-resistant temperature is a temperature at which the substrate will not deform even if it is exposed during the processing process of forming a pattern of the resin film on the substrate. For the resin film, it will change depending on the degree of stretching treatment, and it is necessary not to exceed the glass transition temperature (Tg) at least. In addition, a substrate on which an electrode of indium tin oxide (ITO) or gold is evaporated or patterned on the resin film can also be exemplified as a substrate.

In addition, as examples of other substrates used in the manufacturing method of the present invention, there can be cited substrates such as glass substrates, silicon wafers, polyimide films, etc., which have high heat resistance in themselves but have thin films with low heat resistance formed on them. As a specific example, there are substrates with organic devices such as organic EL (Organic Light-Emitting Diode (OLED)) or organic thin film transistors (TFT) formed on glass, silicon wafers, or polyimide films. Furthermore, the heat resistance temperature of the low heat-resistant substrates such as resin films or substrates with organic devices that are the objects of the present invention also varies depending on the type of resin or the device, and the heat resistance temperature of the substrate used is preferably 80°C to 140°C. Furthermore, the term "substrate with organic device" includes a substrate on which a protective film or a protective thin film is formed after an organic device is formed. This is because even if the heat resistance of these protective films or protective thin films themselves is 150°C or higher, in order to ensure the function of the organic device, they are equivalent to substrate with organic device if the heat resistance is substantially 140°C or lower.

As a method for applying a solution of a photosensitive resin composition on these substrates, in addition to the known solution immersion method and spray method, any method using a roll coater, a disc coater (Land coater machine), a slit coater or a rotary machine can also be adopted. After applying to the desired thickness using these methods, the solvent is removed (pre-baking) to form a film. Pre-baking is performed by heating using an oven, a heating plate, etc. The heating temperature and heating time in pre-baking are appropriately selected according to the solvent used, for example, at a temperature of 60°C to 110°C (set in a manner not to exceed the heat resistance temperature of the substrate) for 1 minute to 3 minutes.

The exposure after pre-baking is performed by using an ultraviolet exposure device, and the exposure is performed through the photoresist, so that only the part of the resist corresponding to the pattern is photosensitized. The exposure device and its exposure conditions are appropriately selected and a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and a far ultraviolet lamp is used for exposure, so that the photosensitive resin composition in the coating is photocured. It is preferred to irradiate a certain amount of light with a wavelength of 365 nm for photocuring.

Alkaline development after exposure is performed for the purpose of removing the resist in the unexposed portion, and the desired pattern is formed by the development. As a developer suitable for the alkaline development, for example, an aqueous solution of carbonate of an alkali metal or alkali earth metal, an aqueous solution of hydroxide of an alkali metal, etc., can be listed. In particular, a weakly alkaline aqueous solution containing 0.05 mass% to 3 mass% of carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, etc. can be used for development at a temperature of 23°C to 28°C, and a commercially available developer or ultrasonic cleaning machine can be used to accurately form a fine image.

After development, it is preferred to perform heat treatment (post-baking) at a temperature of 80°C to 140°C (set in a manner that does not exceed the heat resistance temperature of the substrate) for 20 minutes to 90 minutes. The post-baking is performed for the purpose of improving the adhesion between the patterned resin film and the substrate. It is performed by heating using an oven, a heating plate, etc., as with the pre-baking. The more preferred range of heat treatment conditions for the post-baking is a temperature of 90°C to 120°C and a heating time of 30 minutes to 60 minutes. The patterned resin film of the present invention is formed through the above steps of the optical development method.

As described above, the manufacturing method of forming a resin film pattern of the present invention can be suitably used for forming a resin film pattern on a substrate having a low heat resistance temperature by exposure, alkaline development, etc., and is particularly suitable when a fine resin film pattern is required. Specifically, when using a substrate with a low heat resistance temperature, it is useful for forming various insulating films, coloring films for color filters, partition wall materials for forming organic EL pixels (for example, when forming RGB using an inkjet method), insulating films for touch screens, and light-shielding films. These substrates with resin film patterns can be used for display devices such as liquid crystals or organic EL, for imaging elements, and for touch screens (the main use is for display and touch screen substrates).

[Examples] The present invention is further described in detail below using examples, but the present invention is not limited to these examples. The description starts with an example of preparing a photosensitive resin composition used in the manufacturing method for forming a resin film pattern of the present invention, and the evaluation results of the properties of the cured product of the photosensitive resin composition are described.

First, (A) the synthesis example of the alkali-soluble resin containing a polymerizable unsaturated group is shown. The evaluation of the resin in the synthesis example is performed as follows. [Solid content concentration] 1 g of the resin solution obtained in the synthesis example is impregnated in a glass filter [weight: W0 (g)] and weighed [W1 (g)]. The weight after heating at 160°C for 2 hours [W2 (g)] is calculated using the following formula. Solid content concentration (weight %) = 100 × (W2-W0) / (W1-W0).

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

[Molecular weight] Measured using a gel permeation chromatograph (GPC) [HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2 columns) + TSKgelSuperH-3000 (1 column) + TSKgelSuperH-4000 (1 column) + TSKgelSuper-H5000 (1 column) [manufactured by Tosoh Corporation], temperature: 40°C, speed: 0.6 ml/min], and the weight average molecular weight (Mw) was calculated using the conversion value of standard polystyrene [PS-oligomer kit manufactured by Tosoh Corporation].

In addition, the abbreviations used in the synthesis examples and comparative synthesis examples are as follows. DCPMA: dicyclopentyl methacrylate GMA: glycidyl methacrylate St: styrene AA: acrylic acid SA: succinic anhydride BPFE: bisphenol fluorene epoxy compound (reaction product of 9,9-bis(4-hydroxyphenyl)fluorene and chloromethyloxycyclopropane) BPDA: 3,3,4,4-biphenyltetracarboxylic dianhydride THPA: tetrahydrophthalic anhydride DMPA: dihydroxymethylpropionic acid IDICA: isophorone diisocyanate PTMA: pentaerythritol tetra(hydroxyacetate) DPHA: mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate AIBN: azobisisobutyronitrile TDMAMP: tris-dimethylaminomethylphenol HQ: hydroquinone TEA: triethylamine TPP: triphenylphosphine BzDMA: benzyl dimethylamine PGMEA: propylene glycol monomethyl ether acetate

[Synthesis Example 1] PGMEA 300 g was added to a 1L four-necked flask with a reflux cooler, and the flask system was replaced with nitrogen and then heated to 120°C. A monomer mixture (a mixture of 10 g of AIBN dissolved in 77.1 g (0.35 mol) of DCPMA, 49.8 g (0.35 mol) of GMA, and 31.2 g (0.30 mol) of St) was added dropwise from a dropping funnel to the flask over 2 hours, and then stirred at 120°C for 2 hours to obtain a copolymer solution. Then, after replacing the air in the flask system with air, 24.0 g of AA (95% of the glycidyl group), 0.8 g of TDMAMP and 0.15 g of HQ were added to the obtained copolymer solution, and stirred for 6 hours at 120°C to obtain a copolymer solution containing polymerizable unsaturated groups. Furthermore, 30.0 g of SA (90% of the molar number of AA added) and 0.5 g of TEA were added to the obtained copolymer solution containing polymerizable unsaturated groups and reacted at 120°C for 4 hours to obtain an alkali-soluble copolymer resin solution (A)-1 containing polymerizable unsaturated groups. The solid content concentration of the resin solution is 46% by mass, the acid value (solid content conversion) is 76 mgKOH/g, and the Mw analyzed by GPC is 5300.

[Synthesis Example 2] BPFE 114.4 g (0.23 mol), AA 33.2 g (0.46 mol), PGMEA 157 g and TEAB 0.48 g were placed in a 500 ml four-necked flask with a reflux cooler, and stirred for 20 hours at 100°C to 105°C for reaction. Then, BPDA 35.3 g (0.12 mol) and THPA 18.3 g (0.12 mol) were placed in the flask, and stirred for 6 hours at 120°C to 125°C for heating to obtain an alkali-soluble resin solution (A)-2 containing a polymerizable unsaturated group. The solid content concentration of the obtained resin solution was 56.1% by mass, the acid value (solid content conversion) was 103 mgKOH/g, and the Mw analyzed by GPC was 3600.

[Synthesis Example 3] In a 500 mL four-necked flask with a reflux cooler, 104.2 g (0.29 mol) of bisphenol A type epoxy compound (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name YD-128, epoxide equivalent = 182), 41.2 g (0.57 mol) of AA, 1.50 g of TPP, and 40.0 g of PGMEA were added, and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. Then, 17.4 g (0.13 mol) of DMPA and 84 g of PGMEA were added to the obtained reaction product and the temperature was raised to 45°C. Next, 61.8 g (0.28 mol) of IDICA was added dropwise while paying attention to the temperature in the flask. After the addition was completed, the mixture was stirred at 75°C to 80°C for 6 hours. Then, 21.0 g (0.14 mol) of THPA was added and stirred at 90°C to 95°C for 6 hours to obtain an alkali-soluble resin solution (A)-3 containing polymerizable unsaturated groups. The solid content concentration of the obtained resin solution was 66.6% by mass, the acid value (solid content conversion) was 61 mgKOH/g, and the Mw analyzed by GPC was 11860.

[Synthesis Example 4] PTMA 20 g (0.19 mol of hydroxyl group), DPHA 212 g (2.12 mol of acrylate group), PGMEA 58 g, HQ 0.1 g, and BzDMA 0.01 g were added to a 1 L four-necked flask and reacted at 60°C for 12 hours to obtain a dendrimer solution (B)-3 having a solid content concentration of 80% by mass. The disappearance of the hydroxyl group was confirmed by iodine titration of the obtained dendrimer. The Mw of the obtained dendrimer was 10,000.

(Preparation of photosensitive resin composition) Regarding the preparation of the photosensitive resin composition when the colorant concentration (Pcon) is 0%, Examples 1 to 14 were prepared in the manner shown in Table 1, and Comparative Examples 1 to 14 were prepared in the manner shown in Table 2. Regarding the preparation of the photosensitive resin composition when Pcon is 20%, Examples 15 to 28 were prepared in the manner shown in Table 3, and Comparative Examples 15 to 28 were prepared in the manner shown in Table 4. Regarding Pcon The preparation of the photosensitive resin composition when Pcon is 40% was prepared in the manner shown in Table 5 for Examples 29 to 42, and in the manner shown in Table 6 for Comparative Examples 29 to 42. Regarding the preparation of the photosensitive resin composition when Pcon is 60%, the preparation of the photosensitive resin composition when Pcon is 60% was prepared in the manner shown in Table 7 for Examples 43 to 56, and in the manner shown in Table 8 for Comparative Examples 43 to 56. The components used in the preparation are as follows, and the values in the table are all parts by mass. (A) Alkali-soluble resin containing polymerizable unsaturated groups: (A)-1: The resin solution obtained in the above-mentioned Synthesis Example 1 (solid content concentration 46.0 mass %) (A)-2: The resin solution obtained in the above-mentioned Synthesis Example 2 (solid content concentration 56.1 mass %) (A)-3: The resin solution obtained in the above-mentioned Synthesis Example 3 (solid content concentration 66.6 mass %) (B) Photopolymerizable monomer: (B)-1: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (M-450 manufactured by Toagosei Co., Ltd., acrylic acid group equivalent 88) (B)-2: A mixture of dipentaerythritol pentaacrylate and pentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd., acrylic acid group equivalent 96-115) (B)-3: Dendrimer solution obtained in Synthesis Example 4 (solid content concentration 80.0 mass %) (C) Epoxy compounds: (C)-1: 3,4-epoxyepoxyhexanecarboxylic acid (3',4'-epoxyepoxyhexyl) methyl ester (Celloxide 2021P manufactured by Daicel, epoxy equivalent 135) (C)-2: Triphenylmethane type epoxy resin (EPPN-501H manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 160) (C) -3: 1,2-epoxy-4-(2-oxohexopropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol ("EHPE3150" manufactured by Daicel, epoxide equivalent 180) (D) Hardeners and hardening accelerators for epoxy compounds: (D)-1: Phthalic anhydride (D)-2: Benzene-1,2,4-tricarboxylic acid-1,2-anhydride (D)-3: PGMEA solution containing 2% by mass of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU(R) manufactured by San-Apro) (E) Photopolymerization initiator: Oxime ester-based photopolymerization initiator (Adekacrus NCI-831 manufactured by ADEKA) (F) Solvent: (F)-1: PGMEA (F)-2: Diethylene glycol methyl ethyl ether (EDM) (G) Colorant: (G)-1: Pigment dispersion of 25% by mass of resin-coated carbon black and 5% by mass of polymer dispersant in PGMEA solvent (solid content concentration 30% by mass) (G)-2: Pigment dispersion of 20% by mass of titanium black and 5% by mass of polymer dispersant in PGMEA solvent (solid content concentration 25% by mass) (H) Surfactant: Megafac 475 (manufactured by DIC Corporation) [Table 1]    Mixing ingredients Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 135.7       135.7          120.5       120.5             (A) -2    111.2       111.2 111.2       98.8       98.8 98.8       (A) -3       93.7          93.7       83.2          83.2 (B) Photopolymerizable monomer    (B) -1 15.6 15.6 15.6             13.9 13.9 13.9                (B) -2          15.6    15.6 15.6          13.9    13.9 13.9    (B) -3             19.5                   17.3       （C）Epoxy    (C) -1 6.98 6.98 6.98 6.98 6.98       13.99 13.99 13.99 13.99 13.99          (C) -2                7.73                   15.48       (C) -3                   7.86                   15.76 (D) Epoxy hardener and hardening accelerator    (D) -1 3.0 3.0 3.0 3.0 3.0       5.97 5.97 5.97 5.97 5.97          (D) -2                2.26 2.12                4.48 4.2    (D) -3 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (E) Photopolymerization initiator    (E) 11.7 11.7 11.7 11.7 11.7 11.7 11.7 10.4 10.4 10.4 10.4 10.4 10.4 10.4 (F) Solvent    (F) -1 322 347 364 322 343 347 364 330 351 367 330 348 351 367    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Table 2]    Mixing ingredients Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparison Example 6 Comparative Example 7 Comparison Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 143.2       143.2          113       113             (A) -2    117.4       117.4 117.4       92.6       92.6 92.6       (A) -3       98.9          98.9       78          78 (B) Photopolymerizable monomer    (B) -1 16.5 16.5 16.5             13.0 13.0 13.0                (B) -2          16.5    16.5 16.5          13.0    13.0 13.0    (B) -3             20.6                   16.2       （C）Epoxy    (C) -1 3.5 3.5 3.5 3.5 3.5       17.48 17.48 17.48 17.48 17.48          (C) -2                3.87                   18.7       (C) -3                   3.94                   19.07 (D) Epoxy hardener and hardening accelerator    (D) -1 1.49 1.49 1.49 1.49 1.49       7.47 7.47 7.47 7.47 7.47          (D) -2                1.12 1.05                6.25 5.88    (D) -3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (E) Photopolymerization initiator    (E) 12.4 12.4 12.4 12.4 12.4 12.4 12.4 9.74 9.74 9.74 9.74 9.74 9.74 9.74 (F) Solvent    (F) -1 319 345 363 319 341 345 358 333 354 368 333 350 356 368    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Table 3]    Mixing ingredients Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 99.4       99.4          84.2       84.2             (A) -2    81.5       81.5 81.5       69.1       69.1 69.1       (A) -3       68.6          68.6       58.2          58.2 (B) Photopolymerizable monomer    (B) -1 11.43 11.43 11.43             9.69 9.69 9.69                (B) -2          11.43    11.43 11.43          9.69    9.69 9.69    (B) -3             14.28                   12.11       （C）Epoxy    (C) -1 7.27 7.27 7.27 7.27 7.27       14.57 14.57 14.57 14.57 14.57          (C) -2                7.46                   14.96       (C) -3                   7.86                   15.25 (D) Epoxy hardener and hardening accelerator    (D) -1                2.52                   5.0 4.71    (D) -2 2.71 2.71 2.71 2.71 2.71    2.12 5.39 5.39 5.39 5.39 5.39          (D) -3 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (E) Photopolymerization initiator    (E) 8.57 8.57 8.57 8.57 8.57 8.57 8.57 7.27 7.27 7.27 7.27 7.27 7.27 7.27 (F) Solvent    (F) -1 286 304 317 286 301 304 317 293 308 319 293 306 308 319    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (G) Coloring agent (dispersion)    (G) -1 80 80 80 80 80 80 80 80 80 80 80 80 80 80 (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Table 4]    Mixing ingredients Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 106.9       106.9          76.6       76.6             (A) -2    87.7       87.7 87.7       62.9       62.9 62.9       (A) -3       73.8          73.8       53          53 (B) Photopolymerizable monomer    (B) -1 12.3 12.3 12.3             8.82 8.82 8.82                (B) -2          12.3    12.3 12.3          8.82    8.82 8.82    (B) -3             15.4                   11.02       （C）Epoxy    (C) -1 3.64 3.64 3.64 3.64 3.64       18.22 18.22 18.22 18.22 18.22          (C) -2                3.74                   18.7       (C) -3                   3.81                   19.07 (D) Epoxy hardener and hardening accelerator    (D) -1                1.25 1.18                6.25 5.88    (D) -2 1.35 1.35 1.35 1.35 1.35       6.73 6.73 6.73 6.73 6.73          (D) -3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (E) Photopolymerization initiator    (E) 9.22 9.22 9.22 9.22 9.22 9.22 9.22 6.61 6.61 6.61 6.61 6.61 6.61 6.61 (F) Solvent    (F) -1 311 297 311 311 299 302 316 297 311 321 297 308 311 321    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (G) Coloring agent (dispersion)    (G) -1 80 80 80 80 80 80 80 80 80 80 80 80 80 80 (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Table 5]    Mixing ingredients Embodiment 29 Embodiment 30 Embodiment 31 Embodiment 32 Embodiment 33 Embodiment 34 Embodiment 35 Embodiment 36 Embodiment 37 Embodiment 38 Embodiment 39 Embodiment 40 Embodiment 41 Embodiment 42 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 63.1       63.1          47.9       47.9             (A) -2    51.7       51.7 51.7       39.3       39.3 39.3       (A) -3       43.6          43.6       33.1          33.1 (B) Photopolymerizable monomer    (B) -1 7.25 7.25 7.25             5.51 5.51 5.51                (B) -2          7.25    7.25 7.25          5.51    5.51 5.51    (B) -3             9.07                   6.89       （C）Epoxy    (C) -1 7.27 7.27 7.27 7.27 7.27       14.57 14.57 14.57 14.57 14.47          (C) -2                7.46                   14.96       (C) -3                   7.61                   15.25 (D) Epoxy hardener and hardening accelerator    (D) -1                2.52 2.37                5.0 4.71    (D) -2 2.71 2.71 2.71 2.71 2.71       5.39 5.39 5.39 5.39 5.39          (D) -3 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (E) Photopolymerization initiator    (E) 5.44 5.44 5.44 5.44 5.44 5.44 5.44 4.13 4.13 4.13 4.13 4.13 4.13 4.13 (F) Solvent    (F) -1 250 261 229 210 259 261 269 257 265 232 217 264 265 272    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (G) Coloring agent (dispersion)    (G) -1 160 160       160 160 160 160 160       160 160 160    (G) -2       200 200                200 200          (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Table 6]    Mixing ingredients Comparative Example 29 Comparative Example 30 Comparative Example 31 Comparative Example 32 Comparative Example 33 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 Comparative Example 39 Comparative Example 40 Comparative Example 41 Comparative Example 42 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 70.6       70.6          40.38       40.38             (A) -2    57.9       57.9 57.9       33.1       33.1 33.1       (A) -3       48.8          48.8       27.9          27.9 (B) Photopolymerizable monomer    (B) -1 8.12 8.12 8.12             4.64 4.64 4.64                (B) -2          8.12    8.12 8.12          4.64    4.64 4.64    (B) -3             10.15                   5.8       （C）Epoxy    (C) -1 3.64 3.64 3.64 3.64 3.64       18.22 18.22 18.22 18.22 18.22          (C) -2                3.74                   18.7       (C) -3                   3.81                   19.07 (D) Epoxy hardener and hardening accelerator    (D) -1                1.25 1.18                6.25 5.88    (D) -2 1.35 1.35 1.35 1.35 1.35       6.73 6.73 6.73 6.73 6.73          (D) -3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (E) Photopolymerization initiator    (E) 6.09 6.09 6.09 6.09 6.09 6.09 6.09 3.48 3.48 3.48 3.48 3.48 3.48 3.48 (F) Solvent    (F) -1 246 259 268 246 257 259 268 260 268 273 260 267 268 273    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (G) Coloring agent (dispersion)    (G) -1 160 160 160 160 160 160 160 160 160 160 160 160 160 160    (G) -2                                           (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Table 7]    Mixing ingredients Embodiment 43 Embodiment 44 Embodiment 45 Embodiment 46 Embodiment 47 Embodiment 48 Embodiment 49 Embodiment 50 Embodiment 51 Embodiment 52 Embodiment 53 Embodiment 54 Embodiment 55 Embodiment 56 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 26.7       26.7          11.64       11.64             (A) -2    21.9       21.9 21.9       9.54       9.54 9.54       (A) -3       18.5          18.5       8.04          8.04 (B) Photopolymerizable monomer    (B) -1 3.08 3.08 3.08             1.34 1.34 1.34                (B) -2          3.08    3.08 3.08          1.34    1.34 1.34    (B) -3             3.85                   1.67       （C）Epoxy    (C) -1 7.27 7.27 7.27 7.27 7.27       14.57 14.57 14.57 14.57 14.57          (C) -2                7.46                   14.96       (C) -3                   7.61                   15.25 (D) Epoxy hardener and hardening accelerator    (D) -1                2.52 2.37                5.0 4.71    (D) -2 2.71 2.71 2.71 2.71 2.71       5.39 5.39 5.39 5.39 5.39          (D) -3 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 (E) Photopolymerization initiator    (E) 2.31 2.31 2.31 2.31 2.31 2.31 2.31 1.0 1.0 1.0 1.0 1.0 1.0 1.0 (F) Solvent    (F) -1 213 218 222 213 217 158 162 220 223 224 220 222 163 164    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (G) Coloring agent (dispersion)    (G) -1 240 240 240 240 240       240 240 240 240 240          (G) -2                300 300                300 300 (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Table 8]    Mixing ingredients Comparative Example 43 Comparative Example 44 Comparative Example 45 Comparative Example 46 Comparative Example 47 Comparative Example 48 Comparative Example 49 Comparative Example 50 Comparative Example 51 Comparative Example 52 Comparative Example 53 Comparative Example 54 Comparative Example 55 Comparative Example 56 (A) Alkaline soluble resin containing unsaturated groups    (A) -1 34.3       34.3          4.08       4.08             (A) -2    28.1       28.1 28.1       3.35       3.35 3.35       (A) -3       23.7          23.7       2.82          2.82 (B) Photopolymerizable monomer    (B) -1 3.95 3.95 3.95             0.47 0.47 0.47                (B) -2          3.95    3.95 3.95          0.47    0.47 0.47    (B) -3             4.93                   0.59       （C）Epoxy    (C) -1 3.64 3.64 3.64 3.64 3.64       18.22 18.22 18.22 18.22 18.22          (C) -2                3.74                   18.7       (C) -3                   3.81                   19.07 (D) Epoxy hardener and hardening accelerator    (D) -1                1.25 1.18                6.25 5.88    (D) -2 1.35 1.35 1.35 1.35 1.35       6.73 6.73 6.73 6.73 6.73          (D) -3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 (E) Photopolymerization initiator    (E) 2.96 2.96 2.96 2.96 2.96 2.96 2.96 0.35 0.35 0.35 0.35 0.35 0.35 0.35 (F) Solvent    (F) -1 210 216 220 210 215 156 160 224 225 225 224 225 165 165    (F) -2 170 170 170 170 170 170 170 170 170 170 170 170 170 170 (G) Coloring agent (dispersion)    (G) -1 240 240 240 240 240       240 240 240 240 240          (G) -2                300 300                300 300 (H) Surfactant    (H) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 [Evaluation] The photosensitive resin compositions of Examples 1 to 56 and Comparative Examples 1 to 56 were used to perform the evaluation described below. The results of Examples 1 to 14 and Comparative Examples 1 to 14 are shown in Table 9, the results of Examples 15 to 28 and Comparative Examples 15 to 28 are shown in Table 10, the results of Examples 29 to 42 and Comparative Examples 29 to 42 are shown in Table 11, and the results of Examples 43 to 56 and Comparative Examples 43 to 56 are shown in Table 12.

<Evaluation of development characteristics (pattern line width and pattern linearity)> Each of the photosensitive resin compositions obtained above was applied to a 125 mm × 125 mm glass substrate (Corning 1737) using a rotary coater so that the film thickness after post-baking was 1.2 μm, and pre-baked at 90°C for 1 minute. After that, the exposure gap was adjusted to 100 μm, and a negative photoresist with line/space = 10 μm/50 μm was applied to the dried coating film, and 50 mJ/ ^cm2 of ultraviolet light was irradiated using an ultra-high pressure mercury lamp with an i-ray irradiance of 30 mW/ ^cm2 to perform a photohardening reaction of the photosensitive portion.

Next, the coated board after exposure was developed at 25°C using a 0.04% potassium hydroxide aqueous solution at a spray pressure of 1 kgf/ ^cm2 for 10 seconds and 20 seconds from the development time (breaktime = BT) when the pattern began to appear, and then sprayed with water at a pressure of 5 kgf/ ^cm2 to remove the unexposed part of the coating and form a resin film pattern on the glass substrate. After that, a hot air dryer was used to perform heat post-baking at 100°C for 60 minutes. The line width of the obtained resin film pattern relative to the mask width of 10 μm line and the pattern linearity were evaluated.

Pattern line width: The pattern line width of the mask width of 10 μm was measured using a length measuring microscope (Nikon "XD-20"), and the case within 10±2 μm was set as ○, and the case outside the range of 10±2 μm was set as ×. Pattern linearity: The 10 μm mask pattern after post-baking was observed under an optical microscope, and the case where no peeling relative to the substrate or saw-toothed pattern edge was confirmed was evaluated as ○, the case where it was confirmed in a part was evaluated as △, and the case where it was confirmed throughout the whole was evaluated as ×. Furthermore, the evaluation of pattern line width and pattern linearity was conducted under BT+10 seconds and BT+20 seconds.

<Evaluation of optical density (OD)/μm> The obtained photosensitive resin composition containing the colorant was applied to a 125 mm×125 mm glass substrate (Corning 1737) using a rotary coater so that the film thickness after post-baking was 1.1 μm, and pre-baked at 90°C for 1 minute. Thereafter, without covering with a negative photoresist, 80 mJ/ ^cm2 of ultraviolet light was irradiated using an ultra-high pressure mercury lamp with an i-ray irradiance of 30 mW/ ^cm2 to perform a photocuring reaction.

Next, the coated board after exposure was developed at 25°C using a 0.05% potassium hydroxide aqueous solution at a spray pressure of 1 kgf/ ^cm2 for 60 seconds, then spray-washed at a pressure of 5 kgf/ ^cm2 , and then post-baked at 120°C for 60 minutes using a hot air dryer. The OD value of the coated board was evaluated using a Macbeth density meter. In addition, the film thickness of the colored film formed on the coated board was measured and the value obtained by dividing the OD value by the film thickness was set as OD/μm.

<Evaluation of Solvent Resistance> The solvent resistance of the formed coating (light-shielding film) was evaluated using a coating plate (glass plate with light-shielding film) made in the same way as in the OD evaluation. The surface was wiped back and forth 20 times with cotton soaked in PGMEA, and the surface condition was observed. If the coating surface was not dissolved and not scratched, it was rated as solvent resistance ○, and if the coating surface was dissolved or softened and scratched, it was rated as solvent resistance ×. In addition, if the dissolution and scratching were limited to individual parts, it was rated as △.

[Table 9] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Comparison Example 1 Comparison Example 2 Comparison Example 3 Comparison Example 4 Comparison Example 5 Comparison Example 6 Comparison Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ △ △ △ △ △ △ △ BT+20 ○ ○ ○ ○ ○ ○ ○ △ △ △ △ △ △ △ Solvent resistance × × × × × × × ○ ○ ○ ○ ○ ○ ○ [Table 10] Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ OD 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26 Comparative Example 27 Comparative Example 28 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ △ △ △ △ △ △ △ BT+20 ○ ○ ○ ○ ○ ○ ○ × × × × × × × OD 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Solvent resistance × × × × × × × ○ ○ ○ ○ ○ ○ ○ [Table 11] Embodiment 29 Embodiment 30 Embodiment 31 Embodiment 32 Embodiment 33 Embodiment 34 Embodiment 35 Embodiment 36 Embodiment 37 Embodiment 38 Embodiment 39 Embodiment 40 Embodiment 41 Embodiment 42 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ OD 2.5 2.5 2.5 2.5 2.5 2.4 2.4 2.5 2.5 2.5 2.5 2.5 2.4 2.4 Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Comparative Example 29 Comparative Example 30 Comparative Example 31 Comparative Example 32 Comparative Example 33 Comparative Example 34 Comparative Example 35 Comparative Example 36 Comparative Example 37 Comparative Example 38 Comparative Example 39 Comparative Example 40 Comparative Example 41 Comparative Example 42 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ △ △ △ △ △ △ △ BT+20 ○ ○ ○ ○ ○ ○ ○ △ △ △ △ △ △ △ Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ × × × × × × × BT+20 ○ ○ ○ ○ ○ ○ ○ × × × × × × × OD 2.5 2.5 2.5 2.5 2.5 2.4 2.4 2.5 2.5 2.5 2.5 2.5 2.4 2.4 Solvent resistance × × × × × × × ○ ○ ○ ○ ○ ○ ○ [Table 12] Embodiment 43 Embodiment 44 Embodiment 45 Embodiment 46 Embodiment 47 Embodiment 48 Embodiment 49 Embodiment 50 Embodiment 51 Embodiment 52 Embodiment 53 Embodiment 54 Embodiment 55 Embodiment 56 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ BT+20 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ OD 4 4 4 4 4 3.8 3.8 4 4 4 4 4 3.8 3.8 Solvent resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Comparative Example 43 Comparative Example 44 Comparative Example 45 Comparative Example 46 Comparative Example 47 Comparative Example 48 Comparative Example 49 Comparative Example 50 Comparative Example 51 Comparative Example 52 Comparative Example 53 Comparative Example 54 Comparative Example 55 Comparative Example 56 Pattern line width BT+10 ○ ○ ○ ○ ○ ○ ○ × × × × × × × BT+20 ○ ○ ○ ○ ○ ○ ○ × × × × × × × Pattern linearity BT+10 ○ ○ ○ ○ ○ ○ ○ × × × × × × × BT+20 ○ ○ ○ ○ ○ ○ ○ × × × × × × × OD 4 4 4 4 4 3.8 3.8 4 4 4 4 4 3.8 3.8 Solvent resistance × × × × × × × ○ ○ ○ ○ ○ ○ ○

Industrial Applicability The photosensitive resin composition of the present invention can form a resin film pattern with a line width of 3 μm to 15 μm, especially 10 μm or less, excellent in developing adhesion or linearity, and good solvent resistance, even if the process of forming the resin film pattern does not include a step of heat curing at a temperature exceeding 140°C. Therefore, a resin film pattern having the above-mentioned characteristics can be formed on a resin film such as PET, PEN, etc. having a heat-resistant temperature of 140°C or less, or on a glass substrate or silicon wafer with an organic device such as an organic EL or an organic TFT. The photosensitive resin composition of the present invention is suitable for setting resin films such as transparent film patterns, insulating film patterns, black matrix, and isolation wall patterns required for forming color filters or organic EL pixels or touch screens on substrates with low heat resistance temperatures. These substrates with resin films can be used in the manufacture of display devices such as liquid crystals or organic LEs, or in the manufacture of solid-state imaging elements such as complementary metal oxide semiconductors (CMOS) and touch screens.

without

without

Claims (7)

A method for producing a substrate with a resin film, characterized in that it is a method for producing a substrate with a resin film by forming a resin film pattern on a substrate having a heat-resistant temperature of 140° C. or less, wherein: a photosensitive resin composition containing components A to F, wherein the total amount of components C and D in the solid component excluding component F is 6% by mass to 24% by mass, and containing one or more curing agents and one or more curing accelerators as component D, wherein the curing agent is an acid anhydride, is used as the photosensitive resin composition for forming the resin film pattern; A photosensitive resin composition, wherein the photosensitive resin composition is applied on a substrate and exposed through a photoresist, and the unexposed part is removed by development, and then heated below 140°C to form a predetermined resin film pattern to manufacture a substrate with a resin film, component A: an alkali-soluble resin containing an unsaturated group, component B: a photopolymerizable monomer having at least two ethylenic unsaturated bonds, component C: an epoxy compound, component D: a curing agent for the epoxy compound, component E: a photopolymerization initiator, and component F: a solvent. A photosensitive resin composition, which is a photosensitive resin composition used in the method for manufacturing a substrate with a resin film as described in claim 1, comprising: component A: an alkali-soluble resin containing an unsaturated group, component B: a photopolymerizable monomer having at least two ethylenic unsaturated bonds, component C: an epoxy compound, component D: a curing agent for an epoxy compound containing an anhydride of a polycarboxylic acid, component E: a photopolymerization initiator, and component F: a solvent, and the total amount of components C and D in the solid component excluding component F is 6% to 24% by mass, and the carboxyl group of the anhydride of the polycarboxylic acid of component D is 0.5 mol to 1.0 mol for 1 mol of the epoxy group of component C, and the component D comprises one or more polycarboxylic acid anhydrides and one or more curing accelerators. The photosensitive resin composition as described in claim 2, wherein the curing accelerator is: 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene, or a salt thereof, and the amount of the curing accelerator added is 0.05 to 2 parts by mass relative to 100 parts by mass of the epoxy compound. A photosensitive resin composition used in the method for manufacturing a substrate with a resin film as described in claim 1, comprising: component A: an alkali-soluble resin containing an unsaturated group, component B: a photopolymerizable monomer having at least two ethylenic unsaturated bonds, component C: an epoxy compound, component D: a hardener for the epoxy compound, component E: a photopolymerization initiator, component F: a solvent, and component G: a colorant containing an organic pigment or an inorganic pigment, and comprising one or more hardeners and one or more hardening accelerators as component D. The photosensitive resin composition as described in claim 4, wherein the coloring agent of component G is a light-shielding material containing an organic black pigment or an inorganic black pigment. The photosensitive resin composition as described in claim 4, wherein an acyl oxime-based photopolymerization initiator having a molar absorption coefficient of 10,000 or more at 365 nm is used as the photopolymerization initiator of component E. The photosensitive resin composition according to claim 6, wherein the photopolymerization initiator of component E is an acyl oxime-based photopolymerization initiator of general formula (1);

R ¹ and R ² independently represent C1-C15 alkyl, C6-C18 aryl, C7-C20 arylalkyl or C4-C12 heterocyclic group, R ³ represents C1-C15 alkyl, C6-C18 aryl or C7-C20 arylalkyl; herein, the alkyl and aryl groups may be substituted by C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkacyl or halogen, and the alkylene part may contain unsaturated bonds, ether bonds, thioether bonds or ester bonds; in addition, the alkyl group may be any type of linear, branched or cyclic alkyl group.