JP6838866B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition, a method for forming a cured film using the photosensitive resin composition, a method for forming a black matrix using the photosensitive resin composition, and a cured product of the photosensitive resin composition. The present invention relates to a cured film made of, a black matrix made of the cured film, and a display device provided with the black matrix.

A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which a pair of electrodes are formed so as to face each other. A color filter having pixels of each color such as red (R), green (G), and blue (B) is formed inside one of the substrates. Then, in this color filter, in order to prevent color mixing of different colors in each pixel and to hide the electrode pattern, the pixels of each of R, G, and B are usually arranged in a matrix so as to partition the pixels. A black matrix is formed.

Generally, color filters are formed by lithographic methods. Specifically, first, a black photosensitive composition is applied to a substrate, exposed to light, and developed to form a black matrix. After that, each of the photosensitive compositions of each color of red (R), green (G), and blue (B) is then repeatedly applied, exposed, and developed to form a pattern of each color at a predetermined position to form a color filter. Form.

As a method for forming a black matrix used in a panel for such a display device, for example, a method using a negative type photosensitive resin composition has been proposed.
Specifically, it has been proposed to use a negative type photosensitive resin composition containing a photopolymerizable compound, a photopolymerization initiator, an acrylic resin fine particle dispersion liquid in which acrylic resin fine particles are dispersed, and a solvent. (See Patent Document 1).

Japanese Unexamined Patent Publication No. 2011-170075

Patent Document 1 proposes the use of resin-coated carbon black as a light-shielding agent to be blended in a negative photosensitive resin composition. When resin-coated carbon black is used as a light-shielding agent, it is easy to form a black matrix having a high resistance value.
However, when resin-coated carbon black is used as a light-shielding agent, it is difficult to form a black matrix having a high optical density (OD).
Further, the black matrix is required to have a shape that does not easily change due to post-baking performed after exposure and development.

In view of the above problems, the present invention presents a cured film composed of a photosensitive resin composition having a high resistance value and optical density and capable of forming a black matrix that does not easily change its shape due to heating, and a cured product of the photosensitive resin composition. An object of the present invention is to provide a black matrix composed of the cured film and a display device including the black matrix.

The present inventors in a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a heat-resistant resin, and (E) a light-shielding agent. , An alkali-soluble resin having a softening point of less than 130 ° C., a heat-resistant resin having a softening point of 130 ° C. or higher, and a light-shielding agent containing carbon black coated with a dye are used. As a result, it was found that the above-mentioned problems could be solved, and the present invention was completed.

A first aspect of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a heat-resistant resin, and (E) a light-shielding agent.
(A) The softening point of the alkali-soluble resin is less than 130 ° C.
(D) The softening point of the heat-resistant resin is 130 ° C. or higher.
(E) The light-shielding agent is a photosensitive resin composition containing carbon black coated with a dye.

A second aspect of the present invention is to apply the photosensitive resin composition according to the first aspect onto a substrate to form a coating film.
Exposing the coating film and
A method for forming a cured film, which comprises post-baking the exposed coating film at 120 to 250 ° C.

A third aspect of the present invention is to apply the photosensitive resin composition according to the first aspect onto a substrate to form a coating film.
Regioselective exposure of the coating film and
Developing the exposed coating film and
A method of forming a black matrix, which comprises post-baking the developed coating film at 120-250 ° C.

A fourth aspect of the present invention is a cured film made of a cured product of the photosensitive resin composition according to the first aspect.

A fifth aspect of the present invention is the cured film according to the fourth aspect, which is a black matrix composed of a patterned cured film.

A sixth aspect of the present invention is a display device including the black matrix according to the fifth aspect.

According to the present invention, a photosensitive resin composition having a high resistance value and an optical density and capable of forming a black matrix that does not easily change its shape due to heating, a cured film made of a cured product of the photosensitive resin composition, and the curing thereof. A black matrix made of a film and a display device including the black matrix can be provided.

<< Photosensitive resin composition >>
The photosensitive resin composition contains (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a heat-resistant resin, and (E) a light-shielding agent. Hereinafter, essential or arbitrary materials contained in the photosensitive resin composition and a method for preparing the photosensitive resin composition will be described.

<(A) Alkali-soluble resin>
The alkali-soluble resin is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate) to form a resin film having a thickness of 1 μm on a substrate, and a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute. A solvent that dissolves in a film thickness of 0.01 μm or more when immersed.
Further, the alkali-soluble resin (A) generally has a low softening point. As the photosensitive resin composition, an alkali-soluble resin (A) having a softening point of less than 130 ° C. is used.
Here, the softening point of the resin is the temperature of the exothermic peak measured by the differential thermal analyzer DTA.

(A) The method for adjusting the softening point of the alkali-soluble resin is not particularly limited. Typically, by setting the molecular weight lower, the softening point of the alkali-soluble resin (A) is adjusted to less than 130 ° C. (A) When the softening point of the alkali-soluble resin is 130 ° C. or higher, an appropriate amount of the alkali-soluble resin having a softening point of less than 130 ° C. is blended with the alkali-soluble resin having a softening point of 130 ° C. or higher (A). ) The softening point of the alkali-soluble resin can be adjusted to less than 130 ° C.

Preferable examples of the (A) alkali-soluble resin include (A1) a resin having a cardo structure. By using a photosensitive resin composition containing (A1) a resin having a cardo structure as (A) an alkali-soluble resin, a cured film having an excellent balance of heat resistance, mechanical properties, solvent resistance, chemical resistance, etc. can be obtained. Easy to form.

The resin having the (A1) cardo structure is not particularly limited, and conventionally known resins can be used. Among them, the resin represented by the following formula (a-1) is preferable.

In the formula ^{(a-1), X} a represents a group represented by the following formula (a-2).

In the above formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and Ra ² independently represents a hydrogen atom or a methyl group, respectively. , ^{W a} represents a group represented by a single bond or the following formula (a-3).

Further, in the above formula ^{(a-1), Y} a represents the residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-). Examples of dicarboxylic acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro. Phthalic anhydride, glutaric anhydride and the like can be mentioned.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride and the like.
Further, in the above formula (a-1), m represents an integer of 0 to 20.

(A1) The mass average molecular weight of the resin having a cardo structure (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene. The same applies in the present specification) is preferably 1000 to 40,000, preferably 2000 to 30000. Is more preferable. Within the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

Since it is easy to form a film having excellent mechanical strength and adhesion to a substrate, a copolymer obtained by at least polymerizing (A2) (a1) unsaturated carboxylic acid is also preferably used as (A) alkali-soluble resin. be able to.

(A1) Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids; And so on. Among these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerizability, alkali solubility of the obtained resin, easy availability, and the like. These (a1) unsaturated carboxylic acids can be used alone or in combination of two or more.

The (A2) copolymer may be a copolymer of (a1) an unsaturated carboxylic acid and (a2) an alicyclic epoxy group-containing unsaturated compound. The (a2) alicyclic epoxy group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic epoxy group. The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. These (a2) alicyclic epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

Specifically, examples of the (a2) alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (a2-1) to (a2-15). Among these, in order to obtain appropriate developability, compounds represented by the following formulas (a2-1) to (a2-5) are preferable, and the following formulas (a2-1) to (a2-3) are used. The compound represented is more preferred.

In the above ^{formulas, R a20} represents a hydrogen atom or a methyl ^{group, R a21} represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon ^{atoms, R a22} is a divalent 1 to 10 carbon atoms It represents a hydrocarbon group, where t represents an integer from 0 to 10. As ^Ra21 , a linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group is preferable. ^{Examples of Ra22} include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, and -CH ₂ -Ph-CH _2- (Ph is (Indicating a phenylene group) is preferable.

The (A2) copolymer contains the (a1) unsaturated carboxylic acid and (a2) the alicyclic epoxy group-containing unsaturated compound, as well as the (a3) alicyclic group-containing unsaturated compound having no epoxy group. It may be copolymerized.
The (a3) alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group and the like. These (a3) alicyclic group-containing unsaturated compounds can be used alone or in combination of two or more.

Specifically, examples of the (a3) alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a3-1) to (a3-7). Among these, compounds represented by the following formulas (a3-3) to (a3-8) are preferable in order to obtain appropriate developability, and the following formulas (a3-3) and (a3-4) are used. The compound represented is more preferred.

In the above formula, Ra ²³ represents a hydrogen atom or a methyl group, Ra ²⁴ represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and Ra ²⁵ represents a hydrogen atom or 1 carbon atom. Shows up to 5 alkyl groups. As ^Ra24 , a single bond, linear or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group and a hexamethylene group are preferable. As R ^a25 , for example, a methyl group and an ethyl group are preferable.

Further, the (A2) copolymer is a fat together with the above (a1) unsaturated carboxylic acid, the above (a2) alicyclic epoxy group-containing unsaturated compound, and the above (a3) alicyclic group-containing unsaturated compound. It may be a polymer of an (a4) epoxy group-containing unsaturated compound having no cyclic group.

Examples of the epoxy group-containing unsaturated compound (a4) include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate. (Meta) Acrylic Acid Epoxide Alkyl Esters; α- such as glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxy heptyl α-ethyl acrylate, etc. Alkyl acrylic acid epoxy alkyl esters; etc. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoint of copolymerization reactivity, strength of the resin after curing, and the like. These (a4) epoxy group-containing unsaturated compounds can be used alone or in combination of two or more.

Further, the (A2) copolymer may be obtained by further polymerizing a compound other than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more.

Examples of (meth) acrylic acid esters include linear or branched chains such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. Alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meta) acrylate; and the like.

Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, and N. Examples thereof include -methyl-N-phenyl (meth) acrylamide and N-hydroxyethyl-N-methyl (meth) acrylamide.

Examples of the allyl compound include allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactate; allyloxyethanol; and the like. Can be mentioned.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether and hydroxyethyl vinyl ether. , Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and other alkyl vinyl ethers; vinyl phenyl ether, vinyl trill ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether. , Vinyl aryl ethers such as vinyl naphthyl ethers and vinyl anthranyl ethers; and the like.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl ballerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, and vinyl fluoride. Examples thereof include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy. Alkylstyrene such as methylstyrene and acetoxymethylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Examples thereof include halostyrene such as dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3-trifluoromethylstyrene.

The proportion of the constituent unit derived from the unsaturated carboxylic acid (a1) in the (A2) copolymer is preferably 1 to 50% by mass, more preferably 5 to 45% by mass.
When the (A2) copolymer contains a structural unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound and the above (a4) structural unit derived from the epoxy group-containing unsaturated compound, (A2). ) The total of the proportion of the constituent units derived from the (a2) alicyclic epoxy group-containing unsaturated compound and the proportion of the constituent units derived from the above (a4) epoxy group-containing unsaturated compound in the copolymer is 71% by mass or more. It is preferably 71 to 95% by mass, more preferably 75 to 90% by mass. In particular, the proportion of the constituent unit derived from the (a2) alicyclic epoxy group-containing unsaturated compound in the (A2) copolymer is preferably 71% by mass or more, and is 71 to 80% by mass. Is more preferable. By setting the proportion of the structural unit derived from the alicyclic epoxy group-containing unsaturated compound (a2) in the above range, the stability over time of the photosensitive resin composition can be further improved.
When the (A2) copolymer contains a structural unit derived from the (a3) alicyclic group-containing unsaturated compound, the (a3) alicyclic group-containing unsaturated compound occupying the (A2) copolymer. The proportion of the derived constituent units is preferably 1 to 30% by mass, more preferably 5 to 20% by mass.

The mass average molecular weight of the (A2) copolymer is preferably 2000 to 20000, more preferably 3000 to 30000. Within the above range, the film-forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

Further, as the (A) alkali-soluble resin, at least (A3) a structural unit derived from the above (a1) unsaturated carboxylic acid and (B) a structural unit having a polymerizable site with a photopolymerizable compound described later are included. To the copolymer having, or (A4) the structural unit derived from the above (a1) unsaturated carboxylic acid, and the above (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) epoxy group-containing unsaturated compound. A resin containing at least a copolymer having a derived structural unit and a structural unit having a polymerizable site with the photopolymerizable compound (B) described later can also be preferably used. When the alkali-soluble resin (A) contains the (A3) copolymer or the (A4) copolymer, the adhesion of the film formed by using the photosensitive resin composition to the substrate and the photosensitive resin composition The mechanical strength of the cured film obtained by using the above can be increased.

The (A3) copolymer and the (A4) copolymer are described as other compounds for the copolymer (A2), such as (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, and vinyl ethers. , Vinyl esters, styrenes and the like may be further copolymerized.

The structural unit having a polymerizable moiety with the (B) photopolymerizable compound is preferably one having an ethylenically unsaturated group as the polymerizable moiety with the (B) photopolymerizable compound. The copolymerization having such a structural unit includes, for the (A3) copolymer, at least a part of the carboxyl groups contained in the polymer containing the structural unit derived from the above (a1) unsaturated carboxylic acid. It can be prepared by reacting the (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) epoxy group-containing unsaturated compound. Further, the (A4) copolymer is composed of the above-mentioned (a1) unsaturated carboxylic acid-derived structural unit, (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) epoxy group-containing unsaturated compound. It can be prepared by reacting at least a part of the epoxy group in the copolymer having the derived structural unit with (a1) unsaturated carboxylic acid.

The proportion of the structural unit derived from the (a1) unsaturated carboxylic acid in the copolymer (A3) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass. The proportion of the structural unit having a polymerizable site with the (B) photopolymerizable compound in the copolymer (A3) is preferably 1 to 45% by mass, more preferably 5 to 40% by mass. When the copolymer (A3) contains each structural unit in such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a film having excellent adhesion to the substrate.

The proportion of the structural unit derived from the (a1) unsaturated carboxylic acid in the copolymer (A4) is preferably 1 to 50% by mass, more preferably 5 to 45% by mass. The proportion of the constituent units derived from the (a2) alicyclic epoxy group-containing unsaturated compound and / or (a4) epoxy group-containing unsaturated compound in the copolymer (A4) is preferably 55% by mass or more, 71. It is more preferably mass% or more, and particularly preferably 71 to 80 mass%.
The proportion of the structural unit having a polymerizable site with the (B) photopolymerizable compound in the copolymer (A4) is preferably 1 to 45% by mass, more preferably 5 to 40% by mass. When the copolymer (A4) contains each structural unit in such a ratio, it is easy to obtain a photosensitive resin composition capable of forming a film having excellent adhesion to the substrate.

The mass average molecular weight of the (A3) copolymer and the (A4) copolymer is preferably 2000 to 50000, and more preferably 5000 to 30000. Within the above range, the film-forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

The content of the alkali-soluble resin (A) is preferably 40 to 85% by mass, more preferably 45 to 75% by mass, based on the solid content of the photosensitive resin composition. Further, in the alkali-soluble resin, the total amount of (A) the content of the alkali-soluble tree, (B) the content of the photopolymerizable compound, and (C) the content of the photopolymerization initiator is 100 mass by mass. When the portion is used, it is preferably blended in the photosensitive resin composition so that the content of the photopolymerizable compound (B) in the photosensitive resin composition is 5 to 50 parts by mass.

<(B) Photopolymerizable compound>
Photopolymerizable compounds include monofunctional compounds and polyfunctional compounds.
Examples of the monofunctional compound include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, and N-methylol ( Meta) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-Methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropylphthalate, Glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3 -Tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivative and the like can be mentioned. These monofunctional compounds can be used alone or in combination of two or more.

On the other hand, as the polyfunctional compound, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylpropantri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Ellisritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxipolyethoxyphenyl) propane, 2-hydroxy-3 -(Meta) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin poly Glycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, ( Examples thereof include polyfunctional compounds such as meth) acrylamide methylene ether, a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacrylic formal. These polyfunctional compounds can be used alone or in combination of two or more.

The content of the photopolymerizable compound (B) is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, based on the solid content of the photosensitive resin composition. Within the above range, it tends to be easy to balance sensitivity, developability, and resolution.

<(C) Photopolymerization Initiator>
The photopolymerization initiator (C) is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specifically, as the photopolymerization initiator, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2 -Methylpropan-1-one, bis (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4- Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl Acetal, benzyldimethylketal, 1-phenyl-1,2-propandion-2- (o-ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4- Dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1 , 2-Benz anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoylperoxide, cumenehydroperoxide, 2-mercaptobenzoimidal, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-( o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5- Triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (ie, Michler's ketone) ), 4,4'-bisdiethylaminobenzophenone (ie, ethylmichler's ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert- Butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzos Beron, pentyl-4-dimethylaminobenzoate, 9-phenylacrine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-) Acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5) -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3) -Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2, 4-Bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s- Examples thereof include triazine, "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", "IRGACURE 907" (trade name: manufactured by BASF), "NCI-831" (trade name: manufactured by ADEKA), and the like. .. These photopolymerization initiators can be used alone or in combination of two or more.

Among these, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. Among the oxime-based photopolymerization initiators, particularly preferable ones are O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazole-3-yl] etanone oxime and etanone. , 1- [9-ethyl-6- (pyrrole-2-ylcarbonyl) -9H-carbazol-3-yl], 1- (O-acetyloxime), and 1,2-octanedione, 1- [4- (Phenylthio)-, 2- (O-benzoyloxime)].

The content of the photopolymerization initiator (C) is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photosensitive resin composition. Within the above range, it is easy to prepare a photosensitive resin composition having both good coatability and curability.

<(D) Heat resistant resin>
The photosensitive resin composition contains a heat-resistant resin having a softening point of 130 ° C. or higher. Since the photosensitive resin composition contains (D) a heat-resistant resin, the cured film formed by using the photosensitive resin composition is not easily deformed by heating.
The softening point of the heat-resistant resin (D) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher. (D) The upper limit of the softening point of the heat-resistant resin is not particularly limited, but is preferably 180 ° C. or lower, more preferably 170 ° C. or lower.
If the softening point of the (D) heat-resistant resin is excessively high, the (D) heat-resistant resin may be difficult to dissolve in the solvent.

Preferable examples of the heat-resistant resin (D) include (D1) novolak resin and (D2) copolymer represented by the formula (d2-1) described later.
Hereinafter, the (D1) novolak resin and the (D2) copolymer will be described.

[(D1) Novolac resin]
As the novolak resin (D1), various novolak resins conventionally blended in the photosensitive resin composition can be used as long as the softening point is 130 or more.
The novolak resin (D1) is preferably one obtained by addition-condensing an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenols") and aldehydes under an acid catalyst.

(Phenols)
Examples of phenols include phenols; cresols such as o-cresol, m-cresol, p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3 , 4-Xylenol, 3,5-Xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, Alkylphenols such as o-butylphenol, m-butylphenol, p-butylphenol, and p-tert-butylphenol; trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol; resorcinol, catechol , Hydroquinone, Hydroquinone Monomethyl Ether, Pyrogalol, and Fluoroglycinol and other polyhydric phenols; Alkyl resorcin, Alkyl catechol, and Alkyl hydroquinone and other alkyl polyhydric phenols ); Α-naphthol; β-naphthol; hydroxydiphenyl; and bisphenol A and the like. These phenols may be used alone or in combination of two or more.

Among these phenols, m-cresol is preferable. The content of the unit derived from m-cresol in the (D1) novolak resin is preferably 50% by mass or more, more preferably 70% by mass or more, and may be 100% by mass. Within the above range, heat resistance is improved. Further, the development characteristics are also good when the (D1) novolak resin has a high molecular weight.

(Aldehydes)
Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like. These aldehydes may be used alone or in combination of two or more.

(Acid catalyst)
Acid catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, acetic acid, diethylsulfate, and paratoluenesulfonic acid; and zinc acetate. Examples include metal salts. These acid catalysts may be used alone or in combination of two or more.

[(D2) copolymer]
The (D2) copolymer is a copolymer represented by the following formula (d2-1).

In the formula (d2-1), a and b indicate the molar content (molar ratio) in the copolymer, and a + b ≦ 1, 0.1 ≦ a ≦ 0.9, 0.1 ≦ b ≦ 0.9. Is. c is 0, 1, or 2.
R ^a , R ^b , R ^c , and R ^d are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. R ^a , R ^b , R ^c , and R ^d may be the same as or different from each other.
A is a unit represented by the following formula (d2a), a unit represented by (d2b), a unit represented by (d2c), a unit represented by (d2d), and a unit represented by (d2e). It is a unit including a unit of the first place or higher selected from the group consisting of.
The unit A is one selected from the group consisting of the unit represented by the formula (d2a), the unit represented by (d2b), the unit represented by (d2c), and the unit represented by (d2e). It is preferable to include the above units.
The copolymer represented by the above formula (d2-1) may contain a unit derived from the norbornene-type monomer represented in the formula (d2-1) and a structural unit other than the unit A.

Wherein (d2a), and formula ^{(d2b), R e, R} f, and ^{R g} are each independently an organic group having 1 to 18 carbon atoms. In the formula (d2e), R ^h is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms.

The copolymer (D2) preferably contains a structural unit represented by the formula (d2a) and a unit represented by the formula (d2c) as the structural unit A, and the unit represented by the formula (d2a). It is more preferable to include the unit represented by the formula (d2b) and the unit represented by the formula (d2c).
In this case, it is easy to adjust the solubility of the photosensitive resin composition in an alkaline developer within an appropriate range.
Further, from the viewpoint of heat resistance and strength of the cured film, the (D2) copolymer preferably contains a unit represented by the formula (d2e) as the unit A.

Examples of the organic group constituting R ^a , R ^b , R ^c , and R ^d include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, an alicyclic group, and a carboxyl group. An organic group having a heterocycle and an organic group having a heterocycle can be mentioned, and can be selected from these.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl. Examples include a group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.
Examples of the alkenyl group include an allyl group, a pentaenyl group, and a vinyl group.
Examples of the alkynyl group include an ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include a phenyl group, a naphthyl group, and an anthrasenyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaline group include a tolyl group and a xylyl group.
Examples of the alicyclic group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the organic group having a heterocycle include an epoxy group and an organic group having an oxetanyl group.

When ^{an alkyl group is contained as R a} , R ^b , R ^c , or R ^d , the film-forming property of the photosensitive resin composition is likely to be improved.
When an ^{aryl group is contained as R a} , R ^b , R ^c , or R ^d , it is easy to suppress excessive film loss of the coating film made of the photosensitive resin composition during development using an alkaline developer.
When an organic group having a carboxyl group or an organic group having a heterocycle is contained as ^{R a} , R ^b , R ^c , or R ^{d, a cured film having excellent heat resistance and strength is likely to be formed.}
From the viewpoint that a cured film having excellent heat resistance is particularly easily formed, the (D2) copolymer is a unit containing an organic group having a carboxyl group as ^Ra , R ^b , R ^c , or R ^{d as unit A.} , R ^a , R ^b , R ^c , or a unit containing an organic group having a heterocycle as ^{R d.}

The above-mentioned alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkalil group, alicyclic group, organic group having a carboxyl group, and organic group having a hetero ring have one or more hydrogen atoms. , May be substituted with a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms is preferable.
Since ^{at least one of R a} , R ^b , R ^c , and R ^d is a haloalkyl group, the dielectric constant of the resin film formed by using the photosensitive resin composition can be reduced.

^{Examples of the organic group constituting Re} , R ^f , and R ^g include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkalil group, an alicyclic group, and a heterocycle. Organic groups can be mentioned.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group and n-hexyl. Examples include a group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.
Examples of the alkenyl group include an allyl group, a pentaenyl group, and a vinyl group.
Examples of the alkynyl group include an ethynyl group.
Examples of the alkylidene group include a methylidene group and an ethylidene group.
Examples of the aryl group include a phenyl group, a naphthyl group, and an anthrasenyl group.
Examples of the aralkyl group include a benzyl group and a phenethyl group.
Examples of the alkaline group include a tolyl group and a xylyl group.
Examples of the alicyclic group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
Examples of the organic group having a heterocycle include an epoxy group and an organic group having an oxetanyl group.

In the above-mentioned alkyl group, alkenyl group, alkynyl group, alkylidene group, aryl group, aralkyl group, alkalil group, alicyclic group, and organic group having a heterocycle, one or more hydrogen atoms are substituted with halogen atoms. You may.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a haloalkyl group in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms is preferable.

Examples of the alkyl group having 1 to 12 carbon atoms constituting R ^h include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. , N-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.
Examples of the cycloalkyl group having 3 to 8 carbon atoms constituting R ^h include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
In addition, ^{one or more hydrogen atoms contained in R h} may be substituted with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The copolymer represented by the above formula (d2-1) is derived from, for example, a repeating unit derived from a norbornene-type monomer represented by the following formula (d3) and maleic anhydride represented by the following formula (d4). It is preferable that the repeating unit is an alternating copolymer in which the repeating units are arranged alternately.
The copolymer represented by the above formula (d2-1) may be a random copolymer or a block copolymer.
The repeating unit derived from maleic anhydride represented by the following formula (d4) is a unit represented by the above formulas (d2a) to (d2d) in A in the above formula (d2-1).
When the copolymer represented by the above formula (d2-1) contains the copolymer represented by the above formula (d2e) as the unit A, for example, among ^Ra , R ^b , R ^c , and R ^d. It is particularly preferable that at least one of the above has a unit derived from a norbornene-type monomer which is an organic group having an oxetane ring.

式（ｄ３）中、ｃは０、１、又は２であり、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ、及びＲ^ｄはそれぞれ独立に、水素原子又は炭素原子数１〜３０の有機基である。

In formula (d3), c is 0, 1, or 2, and ^Ra , R ^b , R ^c , and R ^d are independently hydrogen atoms or organic groups having 1 to 30 carbon atoms.

The mass average molecular weight of the heat-resistant resin (D) described above is preferably 10,000 or more, more preferably 20,000 or more. (D) When the mass average molecular weight of the heat-resistant resin is 10,000 or more, it is particularly easy to form a cured film that is not easily deformed by heat by using the photosensitive resin composition.

The content of the heat-resistant resin (D) in the photosensitive resin composition is preferably 0.1 to 5% by mass, more preferably 0.3 to 1% by mass, based on the mass of the solid content of the photosensitive resin composition. preferable. (D) If the content of the heat-resistant resin is too small, the cured film formed by using the photosensitive resin composition is easily deformed by heat. (D) If the content of the heat-resistant resin is excessive, the developability of the photosensitive resin composition may deteriorate.

<(E) Shading agent>
(E) The light-shielding agent contains carbon black (dye-coated CB) coated with a dye. Therefore, the cured film formed by using the photosensitive resin composition has both a high resistance value and a high optical density (OD).
On the other hand, when the photosensitive resin composition contains the dye-coated CB as a light-shielding agent, the cured film formed by using the photosensitive resin composition is easily deformed by heating.
However, since the photosensitive resin composition contains the above-mentioned heat-resistant resin (D), even if the photosensitive resin composition contains the dye-coated CB, the deformation of the cured film due to heating is suppressed.

(Dye-coated CB)
The type of carbon black used as a raw material for the dye coating raw material CB is not particularly limited. For example, known carbon blacks such as lamp black, acetylene black, thermal black, channel black, and furnace black can be used.

The average primary particle size of the raw material carbon black is preferably 5 to 60 nm, more preferably 10 to 50 nm, and particularly preferably 20 to 45 nm. Here, the average primary particle size means an arithmetic mean value of the primary particle size obtained by observing 1500 carbon black primary particles with an electron microscope. If the average primary particle size of the raw material carbon black is too small, agglutination is likely to occur, the stability of the mill base is deteriorated, and dispersion at a high concentration is difficult. On the other hand, if the average primary particle size of the raw material carbon black is excessive, the cured film (for example, black matrix) formed by using the photosensitive resin composition tends to have a shape defect, and a cured film having a rough surface is formed. Cheap.

The DBP oil absorption of the raw material carbon black is preferably 100 ml / 100 g or less. Here, the amount of DBP oil absorbed refers to the capacity of dibutyl phthalate (DBP) absorbed by 100 g of carbon black (JIS6217). If the amount of DBP oil absorbed by the raw material carbon black is excessive, the viscosity of the photosensitive resin composition is increased and the coatability is deteriorated accordingly, and the OD and resistance value of the cured film are likely to decrease.

The pH value of the raw material carbon black is preferably 2 to 10, more preferably 5 to 9, and particularly preferably 4 to 8. Here, the pH value means a value obtained by measuring a mixed solution of carbon black and distilled water with a glass electrode pH meter (JIS6221). If the pH value of the raw material carbon black is too low, the stability of the dye-coated CB tends to deteriorate, and if the pH value is excessive, film peeling tends to occur.

The ash content of the raw material carbon black is preferably 1.0% or less. The specific surface area of the raw material carbon black ^{is preferably 20 to 300 m 2} / g.
If the ash content is excessive, the resistance value of the cured film tends to decrease. If the specific surface area is too small, the shape of the cured film is likely to be defective, and if it is too large, a large amount of dispersant, resin, dye, etc. is required, which is disadvantageous in terms of the production cost of the dye-coated CB.

The raw material carbon black is preferably subjected to an oxidation treatment before being coated with a dye to have at least one type of acidic functional group on the surface, and a plurality of types of oxidation treatments are applied to the surface of two or more types. It is more preferable to have an acidic functional group of.
The raw material carbon black that has not been oxidized has no acidic functional groups on its surface or has an insufficient number of acidic functional groups. Therefore, the dispersibility of the obtained dye-coated CB cannot be sufficiently ensured, and the resistance is high. It is difficult to form a hardened film.
Examples of such an oxidation treatment include a method using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitric oxide gas, nitrogen dioxide gas, anhydrous sulfuric acid, fluorine gas, concentrated sulfuric acid, nitric acid, and various peroxides. Be done.
Acidic functional groups generated by acid or treatment include hydroxyl groups, oxo groups, hydroperoxy groups, carbonyl groups, carboxyl groups, peroxycarboxylic acid groups, aldehyde groups, ketone groups, nitro groups, nitroso groups, amide groups, and imide groups. Examples thereof include a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a thiocarboxylic acid group, a chlorosyl group, a chloryl group, a perchloryl group, an iodosyl group, and an iodil group.

The dye used for producing the dye-coated carbon black is not particularly limited as long as it can be adsorbed on the surface of the carbon black, and known basic dyes, acid dyes, direct dyes, reactive dyes and the like can be used. It can be used.
Anionic or nonionic dyes are used because the sulfone group and carboxy group interact with the functional group on carbon black, the amino group reacts with the alkali-soluble resin, and the dye can be insolubilized with a sulfuric acid band or the like. It can be used more preferably.
From the viewpoint of easily forming a cured film having a high light-shielding property, it is preferable to use a dark-colored dye close to black.

Specific examples of such dyes include
Food Black No. 1. Food Black No. 2. Food Red No. 40, Food Blue No. 1. Food Yellow No. 7th grade food dyes;
BASFID Red 2BMN, BASFID Black X34 (BASF X-34) (BASF), Kayanol Red 3BL (Nippon Kayaku Company), Dermacarbon 2GT (Sandoz), Telon , BASF ID Black X34 (BASF X-34) (BASF), BASF id Blue 750 (BASF), Bernacid Red (Bemcolors, Poughkeepsie, NY), BASF Basacid 28 Acid dyes of each color such as;
Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine (TM) dye (Bayer Chemicals Corporation, Pittsburgh, manufactured by PA Inc.), Cartasol Yellow GTF Presscake (Sandoz, manufactured by Inc Co.); Cartasol Yellow GTF Liquid Special 110 (Sandoz, Inc.); Yellow Shade 16948 (Tricon), Direct Brilliant Pink B (Cropton & Novartis), Carta Black2GT (Sandoz, Sandoz, Inc.), Carta Black2GT (Sandoz, Inc.) Trademark Brilliant Yellow 4GF (manufactured by Sandoz); Pergasol Brilliant CGP (manufactured by Ciba-Geigy), Pittsburgh Black BG (manufactured by JCI), Diazole Black Ltd. Y. Direct dyes of each color such as 34;
Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI), Drimarene Brilliant Red X-2B (Reactive Red 56) (Reactive Red 56) (Pylam) -4B, Levafix Brilliant Red F-6BA, and similar Levafix® days Dyestar L. et al. P. (Charlotte, NC) dyes, Procyon Red H8B (Reactive Red 31) (JCI America), and other reactive dyes of each color;
Neozapon Red 492 (manufactured by BASF), Orasol Red G (manufactured by Ciba-Geigy), Aizen Spiron RedC-BH (manufactured by Hodogaya Chemical Company), Spirit Fast ), Orasol Black RL (manufactured by Ciba-Geigy), Orasol Black RLP (manufactured by Ciba-Geigy), Savinyl Black RLS (manufactured by Sandoz), Orasol Blue GN (manufactured by Ciba-Geoly) ), Oil-soluble dyes such as Morfast Black Concentrate A (manufactured by Morton-Tiocol), and the like. These may be used alone or in combination of two or more.

The content of the dye in the dye-coated CB is preferably 0.5 to 10% by mass, more preferably 1 to 7% by mass, and particularly preferably 1 to 5% by mass. If the dye content is too low, the carbon black coating is insufficient, and it is difficult to form a high-resistance cured film. If the content of the dye is excessive, the excess dye inhibits the dispersion of the dye-coated CB, and thickening of the photosensitive resin composition and aggregation of the dye-coated CB are likely to occur.

In the dye-coated CB, the dye existing on the surface of the dye-coated CB is preferably raked with a metal or a metal salt.
By such rake formation, the dye is fixed to the surface of carbon black or the acidic functional group via a metal or a metal salt, and the dye is hard to be separated from the surface of carbon black.
Therefore, when the dye is raked, it is difficult for the dye to elute and it is easy to form a cured film having a high OD.
Examples of the metal or metal salt used for such rake formation include aluminum, magnesium, calcium, strontium, barium or manganese, or hydrochlorides and sulfates thereof. These metals or metal circles can be used alone or in combination of two or more.
The amount of the metal or metal salt added for rake formation is preferably 0.3 times mol or more, more preferably 0.5 times mol or more, and particularly preferably 0.8 times mol or more with respect to the dye.
If the amount of the metal or metal salt added is too small, the dye is not sufficiently fixed and easily separated from the carbon black surface, the stability of the mill base is poor, and the resistance value is also lowered, which is not preferable.

Next, a method for producing the dye-coated CB will be described. First, the raw material carbon black is mixed with water (prepared by appropriately mixing ion-exchanged water with tap water so that the electrical conductivity is constant, the same applies hereinafter) to form a slurry, and the carbon black is heated and stirred for a predetermined time. Is washed, cooled, and then washed again with water. Next, water is added to the obtained carbon black to form a slurry again, the above-mentioned oxidizing agent is added, and the mixture is stirred at a predetermined temperature for a predetermined time to oxidize the surface of the carbon black and wash with water. The oxidation treatment is carried out a plurality of times as necessary by changing the type of the oxidizing agent. Next, the obtained oxidized carbon black was mixed with water to form a slurry again, and a dye was added to the target dye-coated CB so as to have the predetermined content, and the temperature was 40 to 90 ° C. for 1 to 5 hours. The surface of the carbon black is agitated to adsorb and coat the dye. Further, an equimolar amount of the above-mentioned metal or metal salt is added to the added dye, and the mixture is stirred at 30 to 70 ° C. for 1 to 5 hours to rake the dye with the metal or metal salt to fix the dye on the surface of carbon black. Let me. Then, by cooling this, washing it with water, and filtering and drying it, the desired dye-coated CB can be obtained.

(Other shading agents)
(E) The light-shielding agent may contain other light-shielding agents other than the dye-coated CB described above, as long as the object of the present invention is not impaired. Other light-shielding agents include uncoated carbon blacks, perylene pigments, lactam pigments, titanium blacks, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, and composites. Various black pigments, regardless of whether they are organic or inorganic, such as oxides, metal sulfides, metal sulfates or metal carbonates, can be mentioned.

As the carbon black, known carbon blacks such as lamp black, acetylene black, thermal black, channel black, and furnace black can be used, but it is preferable to use channel black having excellent light-shielding properties. Further, resin-coated carbon black may be used.

As the carbon black, carbon black that has been subjected to a treatment for introducing an acidic group is also preferable. The acidic group introduced into carbon black is a functional group that exhibits acidity as defined by Bronsted. Specific examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like. The acidic group introduced into the carbon black may form a salt. The cation forming a salt with the acidic group is not particularly limited as long as the object of the present invention is not impaired. Examples of the cation include various metal ions, cations of nitrogen-containing compounds, ammonium ions and the like, and alkali metal ions such as sodium ion, potassium ion and lithium ion, and ammonium ion are preferable.

Among the carbon blacks that have been subjected to the treatment for introducing the acidic groups described above, the carboxylic acid groups and carboxylic acids are low in the relative dielectric constant of the light-shielding cured film formed by using the photosensitive resin composition. Carbon black having one or more functional groups selected from the group consisting of a base, a sulfonic acid group, and a sulfonic acid base is preferable.

The method for introducing an acidic group into carbon black is not particularly limited. Examples of the method for introducing an acidic group include the following methods.
1) A method of introducing a sulfonic acid group into carbon black by a direct substitution method using concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, etc., or an indirect substitution method using sulfite, hydrogen sulfite, etc.
2) A method of diazo-coupling an organic compound having an amino group and an acidic group with carbon black.
3) A method in which an organic compound having a halogen atom and an acidic group and carbon black having a hydroxyl group are reacted by Williamson's etherification method.
4) A method of reacting an organic compound having a halocarbonyl group and an acidic group protected by a protecting group with carbon black having a hydroxyl group.
5) A method of deprotecting carbon black after conducting a Friedel-Crafts reaction using an organic compound having a halocarbonyl group and an acidic group protected by a protecting group.

Among these methods, method 2) is preferable because the process of introducing an acidic group is easy and safe. As the organic compound having an amino group and an acidic group used in the method 2), a compound in which an amino group and an acidic group are bonded to an aromatic group is preferable. Examples of such compounds include aminobenzenesulfonic acids such as sulfanilic acid and aminobenzoic acids such as 4-aminobenzoic acid.

The number of moles of acidic groups introduced into carbon black is not particularly limited as long as the object of the present invention is not impaired. The number of moles of acidic groups introduced into carbon black is preferably 1 to 200 mmol, more preferably 5 to 100 mmol, based on 100 g of carbon black.

The carbon black into which an acidic group has been introduced may be coated with a resin.
When a photosensitive resin composition containing carbon black coated with a resin is used, it is easy to form a light-shielding cured film having excellent light-shielding properties and insulating properties and low surface reflectance. The coating treatment with the resin does not cause any adverse effect on the dielectric constant of the light-shielding cured film formed by using the photosensitive resin composition. Examples of resins that can be used for coating carbon black include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, and polystyrene, polycarbonate, polyethylene terephthalate, and poly. Examples thereof include thermoplastic resins such as butylene terephthalate, modified polyphenylene oxide, polysulphon, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylensulphon, polyarylate, and polyether ether ketone. The coating amount of the resin on the carbon black is preferably 1 to 30% by mass with respect to the total of the mass of the carbon black and the mass of the resin.

Further, a perylene-based pigment is also preferable as the light-shielding agent. Specific examples of the perylene-based pigment include a perylene-based pigment represented by the following formula (e-1), a perylene-based pigment represented by the following formula (e-2), and a perylene-based pigment represented by the following formula (e-3). Perylene-based pigments can be mentioned. As commercially available products, product names K0084 and K0083 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene-based pigments.

式（ｅ−１）中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に炭素原子数１〜３のアルキレン基を表し、Ｒ^ｅ３及びＲ^ｅ４は、それぞれ独立に、水素原子、水酸基、メトキシ基、又はアセチル基を表す。

In the formula (e-1), R ^e1 and R ^e2 each independently represent an alkylene group having 1 to 3 carbon atoms, and R ^e3 and R ^e4 independently represent a hydrogen atom, a hydroxyl group, a methoxy group, or a hydrogen atom, respectively. Represents an acetyl group.

式（ｅ−２）中、Ｒ^ｅ５及びＲ^ｅ６は、それぞれ独立に、炭素原子数１〜７のアルキレン基を表す。

In formula (e-2), R ^e5 and R ^e6 each independently represent an alkylene group having 1 to 7 carbon atoms.

式（ｅ−３）中、Ｒ^ｅ７及びＲ^ｅ８は、それぞれ独立に、水素原子、炭素原子数１〜２２のアルキル基であり、Ｎ，Ｏ、Ｓ、又はＰのヘテロ原子を含んでいてもよい。Ｒ^ｅ７及びＲ^ｅ８がアルキル基である場合、当該アルキル基は、直鎖状であっても、分岐鎖状であってもよい。

In formula (e-3), R ^e7 and R ^e8 are independently alkyl groups having a hydrogen atom and 1 to 22 carbon atoms, and may contain heteroatoms of N, O, S, or P, respectively. Good. When R ^e7 and R ^e8 are alkyl groups, the alkyl groups may be linear or branched.

The compound represented by the above formula (e-1), the compound represented by the formula (e-2), and the compound represented by the formula (e-3) are, for example, JP-A-62-1753. , No. 63-26784 can be synthesized by using the method described in Japanese Patent Publication No. 63-26784. That is, a heating reaction is carried out in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride or amines as raw materials. Then, the desired product can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent thereof.

In order to disperse the perylene-based pigment well in the photosensitive resin composition, the average particle size of the perylene-based pigment is preferably 10 to 1000 nm.

The light-shielding agent (E) may contain a pigment having a hue such as red, blue, green, or yellow in addition to the above-mentioned black pigment or purple pigment for the purpose of adjusting the color tone. The pigments having other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, as the pigments having other hues of black pigments and purple pigments, the above-mentioned various pigments can be used. The amount of the pigment having a hue other than the black pigment and the purple pigment is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total mass of the light-shielding agent.

Further, as another light-shielding agent, an inorganic pigment and an organic pigment may be used in combination. The inorganic pigment and the organic pigment may be used alone or in combination of two or more, but when they are used in combination, the organic pigment is in the range of 10 to 80% by mass with respect to the total mass of the inorganic pigment and the organic pigment. It is preferable to use it in the range of 20 to 40% by mass, and it is more preferable to use it in the range of 20 to 40% by mass.

(E) In order to uniformly disperse the light-shielding agent in the photosensitive resin composition, a dispersant may be further used. As such a dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. As the dispersant, it is particularly preferable to use an acrylic resin-based dispersant.

(E) The content of the dye-coated CB in the light-shielding agent is not particularly limited as long as it does not impair the object of the present invention. The content of the dye-coated CB in the (E) light-shielding agent is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and 100% by mass with respect to the mass of the (E) light-shielding agent. % Is the most preferable.

The amount of the (E) light-shielding agent used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically 5 with respect to the mass of the solid content in the photosensitive resin composition. ~ 70% by mass is preferable, and 25 to 60% by mass is more preferable.

<(F) Silane coupling agent>
The photosensitive resin composition may contain (F) a silane coupling agent. (F) The silane coupling agent binds or interacts with various components contained in the photosensitive resin composition via an alkoxy group and / or a reactive group bonded to a silicon atom, or supports a substrate or the like. It binds to the surface of. Therefore, when the (F) silane coupling agent is added to the photosensitive resin composition, the exposed portion is cured satisfactorily, so that it is easy to suppress the generation of suspended matter and development residue after development, and the adhesion to the substrate is improved. It is easy to form an excellent black film.

The silane coupling agent is not particularly limited. Preferable examples of silane coupling agents are methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxy. Monoalkyltrialkoxysilanes such as silane, n-butyltriethoxysilane; dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; monophenyltrialkoxysilanes such as phenyltrimethoxysilane and phenyltriethoxysilane; diphenyldimethoxy. Diphenyldialkoxysilanes such as silane and diphenyldiethoxysilane; monovinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacry (Meta) acryloxyalkyl monoalkyldialkoxysilanes such as loxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane; (meth) acryloxyalkyltrialkoxysilanes such as 3-acryloxypropyltrimethoxysilane; 3 Amino groups such as −aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane Containing trialkoxysilane; non-alicyclic epoxy group-containing alkyltrialkoxysilane such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane; 3-glycidoxypropylmethyldiethoxysilane, etc. Non-alicyclic epoxy group-containing alkyl monoalkyldialkoxysilane; alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epylcyclohexyl) ethyltriethoxysilane Containing alkyltrialkoxysilane; alicyclic epoxy group-containing alkylmonoalkyldialkoxysilane such as 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane; [(3-ethyl-3-oxetanyl) methoxy] propyltri Oxetanyl group-containing alkyltrialkoxysilanes such as methoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane Mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; mercaptoalkylmonoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane; ureidoalkyltrialkoxysilanes such as 3-ureidopropyltriethoxysilane; 3- Alkoxyalkyltrialkoxysilanes such as isocyanatepropyltriethoxysilane; alkyltrialkoxysilanes containing acid anhydride groups such as 3-trimethoxysilylpropyl succinate; Nt-butyl-3- (3-trimethoxysilylpropyl) ) An imide group-containing alkyl trialkoxysilane such as imide succinate; and the like. These silane coupling agents may be used alone or in combination of two or more.

Further, the compound represented by the following formula (F1) is also preferably used as a silane coupling agent.
R ^F1 _d R ^F2 _(3-d) Si-R ^F3- NH-C (O) -Y ^F- R ^F4- X ^F ... (F1)
(In the formula (F1), R ^F1 is an alkoxy group, R ^F2 is an alkyl group, d is an integer of 1 to 3, R ^F3 is an alkylene group, and Y ^F is -NH-, -O. -, or -S- and and, R ^F4 is a single bond, or an alkylene group, X ^F is a nitrogen-containing heteroaryl group with multilingual ring monocyclic may be substituted group, X ^-Y F ^{-R F4} in ^F - is ring bonded with a nitrogen-containing 6-membered aromatic ^ring, -Y F ^{-R F4} - is bonded to the carbon atoms of the nitrogen-containing 6-membered aromatic in the ring).

In formula (F1), ^RF1 is an alkoxy group. For R ^F1, number of carbon atoms in the alkoxy group 1 to 6, more preferably 1 to 4, from the viewpoint of the reactivity of the silane coupling agent 1 or 2 are particularly preferred. Preferred examples of R ^F1 is a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group, isobutoxy group, sec- butoxy group, tert- butoxy group, n- pentyloxy group, and n -Hexyloxy group is mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable.

By silanol groups is an alkoxy group R ^F1 is generated are hydrolyzed to react with the surface of the substrate, adhesion to the surface of the support substrate or the like of the coating film formed by using the photosensitive resin composition It is easy to improve the sex. Therefore, d is preferably 3 from the viewpoint of easily improving the adhesion of the coating film to the surface of the support such as the substrate.

In formula (F1), ^RF2 is an alkyl group. For R ^F2, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, from the viewpoint of the reactivity of the silane coupling agent 1 or 2 are particularly preferred. ^{Preferred specific examples of RF2} are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group. , N-Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

In formula (F1), ^RF3 is an alkylene group. For R ^F3, number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 6, 2 to 4 are particularly preferred. Preferred examples of R ^F3 are methylene, 1,2-ethylene, 1,1-ethylene, propane-1,3-diyl, propane-1,2-diyl group, propane-1,1 Diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane- 2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, and hexane-1,6-diyl group, heptane-1,7- Diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, and dodecane-1,12-diyl group. Be done. Among these alkylene groups, 1,2-ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group are preferable.

Y ^F is -NH -, - O-, or a -S-, is preferably -NH-. -CO-O-, or -CO-S- than bond represented by, for towards the bond represented by -CO-NH- is less subject to hydrolysis, the silane compound ^{Y F} is -NH- When a photosensitive resin composition contained as a coupling agent is used, a coating film having excellent adhesion to a support such as a substrate can be formed.

^RF4 is a single bond or an alkylene group, preferably a single bond. Preferred example of R ^F4 is an alkylene group ^are the same as ^{R F3.}

X ^F is substituted a nitrogen-containing heteroaryl group with multilingual ring is good monocyclic, -Y F ^-R F4 in X ^{F -} and binding to ring nitrogen-containing 6-membered aromatic ring in ^and, -Y F ^{-R F4} - it is bonded to a carbon atom of the nitrogen-containing 6-membered aromatic ring. Reason is unknown, the use of a photosensitive resin composition containing a compound having such a X ^F as the silane coupling agent, to form a coating film having excellent adhesiveness to a support such as a substrate.

When ^XF is a polycyclic heteroaryl group, the heteroaryl group may be a group in which a plurality of monocycles are condensed, or a group in which a plurality of monocycles are bonded via a single bond. When X ^F is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 to 3. When X ^F is a polycyclic heteroaryl group, the ring fused or bonded to the nitrogen-containing 6-membered aromatic ring in ^{X F may or may not contain a hetero atom, and is an aromatic ring.} Does not have to be an aromatic ring.

Examples of the nitrogen-containing heteroaryl group X ^F substituent which may be have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms , Alkenyloxy group with 2 to 6 carbon atoms, aliphatic acyl group with 2 to 6 carbon atoms, benzoyl group, nitro group, nitroso group, amino group, hydroxy group, mercapto group, cyano group, sulfonic acid group, carboxyl Groups, halogen atoms and the like can be mentioned. The number of the substituents X ^F has is not particularly limited within a range not inhibiting the object of the present invention. The number of substituents contained in X ^F is preferably 5 or less, and more preferably 3 or less. When X ^F has a plurality of substituents, the plurality of substituents may be the same or different.

Preferred examples of X ^F, include groups of the following formulas.

Among the above groups, groups of formula are preferred as X ^F.

Preferable specific examples of the compound represented by the formula (F1) described above include the following compounds 1 to 8.

The content of the (F) silane coupling agent in the photosensitive resin composition is not particularly limited. The content of the silane coupling agent (F) is preferably 1000 to 10000 mass ppm, more preferably 1500 to 9000 mass ppm, and particularly preferably 2000 to 8000 mass ppm, based on the total mass of the photosensitive resin composition.

<(S) solvent>
The photosensitive resin composition preferably contains the solvent (S) for the purpose of adjusting the coatability and the like.

Preferable examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono. -N-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono- n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. (Poly) alkylene glycol monoalkyl ethers; (poly) such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. ) Alkylene glycol monoalkyl ether acetates; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; 2-hydroxypropionic acid Lactate alkyl esters such as methyl and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybu Tylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n butyrate Other esters such as -propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, xylene Such as aromatic hydrocarbons and the like. These solvents can be used alone or in combination of two or more.

The solvent (S) may contain a nitrogen-containing polar organic solvent in addition to the above solvent. When the solvent (S) contains a nitrogen-containing polar organic solvent, a fine pattern is easily formed, and the adhesion of the formed pattern to the substrate is improved.

（式（Ｓ１）中、Ｒ^Ｓ１及びＲ^Ｓ２は、それぞれ独立に炭素原子数１〜３のアルキル基であり、Ｒ^Ｓ３は下式（Ｓ１−１）又は下式（Ｓ１−２）：

で表される基である。式（Ｓ１−１）中、Ｒ^Ｓ４は、水素原子又は水酸基であり、Ｒ^Ｓ５及びＲ^Ｓ６は、それぞれ独立に炭素原子数１〜３のアルキル基である。式（Ｓ１−２）中、Ｒ^Ｓ７及びＲ^Ｓ８は、それぞれ独立に水素原子、又は炭素原子数１〜３のアルキル基である。）
で表される化合物が挙げられる。（Ｓ）溶剤は、２種以上の含窒素極性有機溶剤を組み合わせて含んでいてもよい。 The solvent (S) may contain various nitrogen-containing polar organic solvents conventionally blended in the photosensitive resin composition. Preferable examples of the nitrogen-containing polar organic solvent include amides such as N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylacetamide, N, N-diethylformamide; 1,3-dimethyl-. Heterocyclic polar organic solvents such as 2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone, γ-butyrolactone; and the following formula (S1):

(In the formula ^{(S1), R S1} and ^{R S2} are each independently an alkyl group having 1 to 3 carbon ^{atoms, R S3} is the following formula (S1-1) or the following formula (S1-2):

It is a group represented by. Wherein ^{(S1-1), R S4} is a hydrogen atom or a hydroxyl ^{group, R S5} and ^{R S6} are each independently an alkyl group having 1 to 3 carbon atoms. Wherein ^{(S1-2), R S7} and ^{R S8} are each independently a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms. )
Examples thereof include compounds represented by. The solvent (S) may contain a combination of two or more kinds of nitrogen-containing polar organic solvents.

Among the above nitrogen-containing polar organic solvents, the compound represented by the formula (S1) is preferable.
Among the compounds represented by formula ^(S1), as a specific example of ^{R S3} is a group represented by the formula (S1-1) is, N, N, 2- trimethyl propionamide, N- ethyl, N , 2-Dimethylpropionamide, N, N-diethyl-2-methylpropionamide, N, N, 2-trimethyl-2-hydroxypropionamide, N-ethyl-N, 2-dimethyl-2-hydroxypropionamide, and Examples thereof include N, N-diethyl-2-hydroxy-2-methylpropionamide.
Among the compounds represented by formula ^(S1), as a specific example of ^{R S3} is a group represented by the formula (S1-2) is, N, N, N ', N'- tetramethyl urea, N , N, N', N'-tetraethylurea and the like.

Among the compounds represented by the formula (S1), N, N, 2-trimethylpropionamide and N, N, N', N'-tetramethylurea are more preferable, and N, N, N', N'- Tetramethylurea is particularly preferred.

(S) The content of the nitrogen-containing polar organic solvent in the solvent is not particularly limited as long as the object of the present invention is not impaired. The lower limit of the content of the nitrogen-containing polar organic solvent in the solvent is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, and most preferably 10% by mass or more. The upper limit of the content of the nitrogen-containing polar organic solvent in the solvent (S) may be appropriately set. For example, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is particularly preferable.

The content of the solvent (S) in the photosensitive resin composition is not particularly limited as long as it does not impair the object of the present invention, and is appropriately considered in consideration of the coatability of the photosensitive resin composition and the film thickness of the coating film. It is determined. Typically, the solvent (S) has a solid content concentration of the photosensitive resin composition of preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and particularly preferably 15 to 30% by mass. Used for.

<Other ingredients>
The photosensitive resin composition may contain a thermal polymerization inhibitor, an antifoaming agent, a surfactant and the like in addition to the components described above.
As the thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether and the like can be used. As the defoaming agent, silicone-based or fluorine-based compounds can be used. As the surfactant, various known thermal polymerization inhibitors such as anionic, cationic and nonionic surfactants can be used.

<Method of preparing photosensitive resin composition>
The photosensitive resin composition typically contains a predetermined amount of (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) heat-resistant resin, and (E). ) The light-shielding agent and, if necessary, other optional components are uniformly dispersed and dissolved in the solvent (S) so as to have a desired solid content concentration.
A photosensitive resin composition may be prepared by using a masterbatch in which the light-shielding agent (E) is concentrated in the solvent (S) in advance.
The obtained photosensitive resin composition may be filtered using a filter having a desired opening diameter.

<< Method of forming a cured film >>
A black cured film is formed by using the photosensitive resin composition described above.
The method for forming the cured film is not particularly limited. As a preferable method for forming a cured film,
By applying the above-mentioned photosensitive resin composition on a substrate to form a coating film,
Exposing the coating film and
Examples thereof include a method including post-baking the exposed coating film at 120 to 250 ° C.

First, the photosensitive resin composition is applied onto a substrate by a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating device such as a spinner (rotary coating device), a curtain flow coater, a die coater, or a slit coater. It is applied using an apparatus to form a coating film.
The material of the substrate is not particularly limited, and a substrate conventionally used for forming a black matrix is preferably used.

After applying the photosensitive resin composition, the coating film is usually dried to remove the solvent. The drying method is not particularly limited, for example, (1) a method of drying on a hot plate at a temperature of 80 ° C. to 120 ° C., preferably 90 ° C. to 100 ° C. for 60 seconds to 120 seconds, and (2) several hours at room temperature. Either a method of leaving the solvent for several days or (3) a method of putting it in a warm air heater or an infrared heater for several tens of minutes to several hours to remove the solvent may be used.

The coating film is then exposed. The exposure may be performed on the entire surface of the coating film or may be performed regioselectively.
When the coating film is exposed in a regioselective manner, the exposure is typically done through a negative mask. When forming a black matrix as a cured film, regioselective exposure is performed according to the pattern of the black matrix.
The coating film is exposed by irradiating it with active energy rays such as ultraviolet rays and excimer laser light. Energy dose to be irradiated may differ depending on the composition of the photosensitive resin composition, for example, about 2000 mJ / cm ² from 30 mJ / cm ² is preferred.

When the exposure is regioselective, the exposed coating film is patterned with an alkaline developer to form a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the alkaline developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium hydroxide.

The cured film formed by full exposure or the developed patterned cured film is post-baked at a temperature of 120-250 ° C. When post-baking is performed at such a temperature, the cured film may be deformed by heat, but when the above-mentioned photosensitive resin composition is used, the deformation of the cured film due to heat is suppressed.

The black cured film formed as described above has a high resistance value and optical density (OD), and the amount of deformation is small even when heated during post-baking.
Such a black cured film is suitably used as a light-shielding material such as a black matrix in panels for various display devices, for example.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

[Preparation Example 1]
First, in a 500 ml four-necked flask, 235 g of bisphenol fluoride type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid. Was charged, and the mixture was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature of the solution was gradually raised while the solution was cloudy, and the solution was heated to 120 ° C. to completely dissolve the solution. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value became less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. Then, it was cooled to room temperature to obtain a colorless and transparent solid bisphenol fluorene type epoxy acrylate represented by the following formula (a-4).

Next, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the above-mentioned bisphenol fluorene type epoxy acrylate thus obtained to dissolve it, and then 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was mixed, gradually heated, and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain resin A-1. The disappearance of the acid anhydride group was confirmed by the IR spectrum. The resin A-1 corresponds to the resin represented by the above formula (a-1). The softening point of the resin A-1 was less than 130 ° C.

[Example 1 and Comparative Examples 1 to 5]
In Examples and Comparative Examples, the resin A-1 obtained in Preparation Example 1 was used as the (A) alkali-soluble resin ((A) component).
Further, in Examples and Comparative Examples, dipentaerythritol hexaacrylate was used as the (B) photopolymerizable compound ((B) component).
As the (C) photopolymerization initiator (component (C)), NCI-831 manufactured by ADEKA Corporation was used.
As the (D) heat-resistant resin (component (D)), a novolak resin D1 (softening point 160 ° C.) having a mass average molecular weight of 30,000 was used, and as the (D') non-heat-resistant resin (component (D')). Used a novolak resin D2 (softening point 112 ° C.) having a mass average molecular weight of 4,000. The content of the unit derived from m-cresol of each novolak resin is 90% by mass.
The following E1 to E3 were used as the (E) light-shielding agent (component (E)). The numerical values of the component (E) in Table 1 indicate only the solid content of each carbon black.
E1: Dispersion solution co-dispersed with dye-coated carbon black E2: Dispersion solution co-dispersed with resin-coated carbon black E3: Dispersion solution co-dispersed with untreated carbon black (S) 3-methoxybutyl acetate as a solvent A mixed solvent consisting of 45% by mass, 10% by mass of cyclohexanone, and 45% by mass of propylene glycol monomethyl ether acetate was used.

The amounts of the (A) component, the (B) component, the (C) component shown in Table 1, the type and amount of the (D) component or the (D') component shown in Table 1, and the types listed in Table 1. And the amount of the component (E) were dispersed and dissolved in the solvent (S) so that the solid content concentration was 20% by mass to obtain the photosensitive resin compositions of Example 1 and Comparative Example 4.
The amount of the component (A), the component (B), and the component (C) shown in Table 1 and the type and amount of the component (E) shown in Table 1 are adjusted so that the solid content concentration is 20% by mass. (S) The photosensitive resin compositions of Comparative Examples 1 to 3 and Comparative Example 5 were obtained by dispersing and dissolving in a solvent.
Using the obtained photosensitive resin composition, the optical density (OD), surface resistance, and thermal deformation of the cured film were evaluated according to the following method. The results of these evaluations are shown in Table 1.

<OD evaluation method>
The photosensitive resin compositions of Examples and Comparative Examples were applied onto an EXG glass substrate manufactured by Corning, and then prebaked at 100 ° C. for 60 seconds to form a coating film having a film thickness of 1.5 μm. The formed coating film was exposed to an exposure amount of 50 mJ / cm ² via a mask. After the exposure, development was carried out by a spray method (23 ° C., 70 seconds) using a KOH aqueous solution having a concentration of 0.04% by mass to obtain a patterned black cured film. The obtained black cured film was post-baked at 230 ° C. for 20 minutes.
The OD of the obtained cured film was measured using D200-II (manufactured by Gretag Mcbeth).

<Surface resistance evaluation method>
The coating film was formed, exposed, and developed in the same manner as in the OD evaluation method. After baking the developed black cured film at 230 ° C. for 180 minutes, the surface resistance of the cured film was measured at a measurement voltage of 1,000 V using Hiresta MCP-HT450 (Probe UR-100 manufactured by Mitsubishi Analytech Co., Ltd.). ..

<Evaluation of thermal deformation (reflow amount)>
The photosensitive resin compositions of Examples and Comparative Examples were applied onto an EXG glass substrate manufactured by Corning, and then prebaked at 100 ° C. for 60 seconds to form a coating film having a film thickness of 1.5 μm. ^{The formed coating film was exposed to an exposure amount of 50 mJ / cm 2} through a mask for forming a pattern having a line portion having a line width of 5 μm. After the exposure, development was carried out by a spray method (23 ° C., 70 seconds) using a KOH aqueous solution having a concentration of 0.04% by mass to obtain a patterned black cured film. The obtained black cured film was post-baked at 230 ° C. for 20 minutes.
By observing the black cured film with an optical microscope, the line width W1 before post-baking and the line width W2 after post-baking are measured for the line portion in the cured film, and the value of W2-W1 is defined as the reflow amount. did.

According to Table 1, a photosensitive resin composition containing carbon black coated with a dye and a heat-resistant resin having a softening point of 130 ° C. or higher has high OD, high surface resistance, and low thermal deformation amount. It can be seen that a cured film showing the above can be formed.

According to Comparative Example 1, when a photosensitive resin composition containing a resin-coated carbon black as a light-shielding agent without containing a heat-resistant resin is used, the OD value of the formed cured film is slightly low and it is easily deformed by heat. I understand.

According to Comparative Example 2, when the amount of the resin-coated carbon black used is increased as compared with Comparative Example 1, it can be seen that the OD value of the cured film is high while the surface resistance of the cured film is low.

According to Comparative Example 3, it can be seen that the cured film is remarkably easily thermally deformed when the photosensitive resin composition containing no heat-resistant resin is used even if it contains carbon black coated with a dye.

According to Comparative Example 4, a photosensitive resin containing carbon black coated with a dye as a light-shielding agent, but containing a non-heat-resistant resin having a softening point of less than 130 ° C. instead of a heat-resistant resin having a softening point of 130 ° C. or higher. When the composition is used, it can be seen that the cured film is remarkably easily thermally deformed as in Comparative Example 3.

According to Comparative Example 5, when a photosensitive resin composition containing carbon black that does not contain a heat-resistant resin and is not surface-treated as a light-shielding agent is used, it can be seen that the surface resistance of the cured film is remarkably low.

Claims (10)

Contains (A) alkali-soluble resin, (B) photopolymerizable compound, (C) photopolymerization initiator, (D) heat-resistant resin, and (E) light-shielding agent.
The softening point of the alkali-soluble resin (A) is less than 130 ° C.
The softening point of the heat-resistant resin (D) is 130 ° C. or higher and 180 ° C. or lower .
The heat-resistant resin (D) contains a novolak resin containing 50% by mass or more of units derived from m-cresol.
A photosensitive resin composition in which the light-shielding agent (E) contains carbon black coated with a dye. The photosensitive resin composition according to claim 1, wherein the content of the heat-resistant resin (D) is 0.1 to 5% by mass with respect to the mass of the solid content of the photosensitive resin composition. The photosensitive resin composition according to claim 1 or 2 , wherein the heat-resistant resin (D) has a mass average molecular weight of 10,000 or more. The photosensitive resin composition according to any one of claims 1 to 3 is applied onto a substrate to form a coating film.
Exposing the coating film and
A method for forming a cured film, which comprises post-baking the exposed coating film at 120 to 250 ° C. The coating film is exposed in a regioselective manner.
Further, including developing the exposed coating film,
The method for forming a cured film according to claim 4 , wherein the post-baking is performed on the developed coating film. The photosensitive resin composition according to any one of claims 1 to 3 is applied onto a substrate to form a coating film.
Regioselective exposure of the coating film and
To develop the exposed coating film and
A method for forming a black matrix, which comprises post-baking the developed coating film at 120 to 250 ° C. A cured film made of a cured product of the photosensitive resin composition according to any one of claims 1 to 3. The cured film according to claim 7 , which is a patterned cured film. A black matrix comprising the patterned cured film according to claim 8. A display device comprising the black matrix according to claim 9.