KR20150075376A - Photosensitive resin composition - Google Patents

Abstract

The present invention is to provide a photosensitive resin composition which can form a pattern having excellent adhesion to a substrate and water resistance; a method for forming the pattern using the photosensitive resin composition; a black matrix formed by using the photosensitive resin composition including a light shielding agent among the photosensitive resin composition as a colorant; and a display device having the black matrix. A silane coupling agent (D) of a specific structure is mixed to the photosensitive resin composition including an alkali soluble resin (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C).

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

A black matrix formed by using a photosensitive resin composition, a pattern forming method using the photosensitive resin composition, a photosensitive resin composition containing a light shielding agent as a colorant in the photosensitive resin composition, and a display device .

The pattern formed using the photosensitive resin composition is used in various electric and electronic devices typified by a display device such as a liquid crystal display device. For example, in a panel for a display device, a black matrix constituting a color filter and a pattern formed by using a photosensitive resin composition as a subpixel of RGB or a black column spacer are used.

As a photosensitive resin composition used for this purpose, for example, a photosensitive resin composition containing an alkali-soluble resin having a specific structure, a photopolymerization initiator, a photopolymerizable monomer, and a colorant is known (Patent Document 1).

Japanese Patent Application Laid-Open No. 2006-079064

The pattern formed by using the photosensitive resin composition used in electric and electronic devices typified by a display device is improved in the adhesion to the substrate and the water resistance that can withstand use under high temperature and high humidity conditions for the purpose of improving the reliability of the operation of the device Is required. The pattern formed by using the photosensitive resin composition described in Patent Document 1 is somewhat superior to the adhesion to the substrate and the water resistance, but further improvement of these properties is required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide a photosensitive resin composition capable of forming a pattern having excellent adhesion to a substrate and water resistance, a pattern forming method using the photosensitive resin composition, And a display device provided with the black matrix. The present invention also provides a display device comprising the black matrix.

The present inventors have conducted intensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by blending a silane coupling agent (D) having a specific structure in a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator And completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent,

(D) a silane coupling agent is a compound represented by the following formula (1).

R ¹ _m R ² _(3-m) Si-R ³ -NH-C (O) -YR ⁴ -X (One)

(In the formula (1), R ¹ is an alkoxy group, R ² is an alkyl group, m is an integer of 1 to 3, R ³ is an alkylene group, Y is -NH-, -O- or -S- , R ⁴ is a single bond or an alkylene group, X is a nitrogen heteroaryl group which may have a substituent or may be a monocyclic or polycyclic ring, a ring bonding with -YR ⁴ - in X is a nitrogen-containing six- ⁴ - is bonded to a carbon atom in the nitrogen-containing six-membered aromatic ring.

According to a second aspect of the present invention, there is provided a process for producing a photosensitive resin composition, comprising the steps of: applying a photosensitive resin composition according to the first aspect onto a substrate to form a coating film;

Selectively exposing the coating film to light;

And developing the exposed coated film.

A third aspect of the present invention is a black matrix formed by using a photosensitive resin composition comprising a light-shielding agent as a coloring agent in the photosensitive resin composition according to the first aspect.

A fourth aspect of the present invention is the display device having the black matrix according to the third aspect.

According to the present invention, there is provided a photosensitive resin composition capable of forming a pattern excellent in adhesiveness to a substrate and water resistance, a pattern forming method using the photosensitive resin composition, and a photosensitive resin composition comprising a light shielding agent as a colorant in the photosensitive resin composition And a display device including the black matrix can be provided.

&Quot; Photosensitive resin composition &

The photosensitive resin composition according to the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent having a specific structure. Hereinafter, essential or optional components included in the photosensitive resin composition according to the present invention will be described in order.

<(A) Alkali-soluble resin>

(A) (hereinafter also referred to as "component (A)") refers to a resin film having a thickness of 1 μm formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by weight And is dissolved in a KOH aqueous solution having a concentration of 0.05% by weight for 1 minute to dissolve in a film thickness of 0.01 탆 or more.

The alkali-soluble resin (A) is not particularly limited as long as it is the above-described alkali-soluble resin, and can be appropriately selected from conventionally known resins. Suitable resins as the (A) alkali-soluble resin include (A1) resins having a cardo structure.

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

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

In formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a represents ^a single bond Or a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue other than an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of dicarboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-undo-methylene tetrahydrophthalic anhydride, anhydrous chloridic acid, methyltetrahydrophthalic anhydride , And anhydrous glutaric acid.

In the formula (a-1), Z ^a represents a residue other than the two acid anhydride groups from the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

In the above formula (a-1), m represents an integer of 0 to 20.

The weight average molecular weight of the resin (A1) having a cardo structure is preferably 1000 to 40000, more preferably 2,000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

As the alkali-soluble resin (A), a copolymer of (a1) an unsaturated carboxylic acid and another copolymerizable component of an unsaturated carboxylic acid may be used. Of these resins, copolymers (A2) in which at least an unsaturated carboxylic acid (a1) and an epoxy group-containing unsaturated compound (a2) are at least polymerized are preferable because a photosensitive resin composition giving a pattern excellent in breaking strength and adhesion to a substrate is easily obtained .

(a1) Examples of the unsaturated carboxylic acid 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; Anhydrides of these dicarboxylic acids; And the like. Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the resin to be obtained, ease of obtaining water, and the like. These (a1) unsaturated carboxylic acids may be used alone or in combination of two or more.

Examples of the epoxy group-containing unsaturated compound (a2) include an unsaturated compound having an alicyclic epoxy group (a2-I) and an unsaturated compound having no alicyclic epoxy group (a2-II) Unsaturated compounds are preferred.

In the unsaturated compound having (a2-I) 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 isobonyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a2-I) alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.

Specifically, examples of the (a2-I) alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (a2-1) to (a2-16). Among them, the compounds represented by the following formulas (a2-1) to (a2-6) are preferable, and the compounds represented by the following formulas (a2-1) to (a2-4) desirable.

Wherein R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10 Represents an integer. R ¹² is preferably a linear or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene. R ¹³ include, for example, methylene group, ethylene group, propylene group, tetramethylene group, ethyl ethylene, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene _{group, -CH 2 - Ph-CH 2} - ( And Ph represents a phenylene group).

Examples of the epoxy group-containing unsaturated compound having no (a2-II) alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (Meth) acrylate, and 7-epoxyheptyl (meth) acrylate; ? -alkylacrylic acid epoxyalkyl esters such as glycidyl? -ethyl acrylate, glycidyl? -n-propyl acrylate, glycidyl? -n-butyl acrylate, and 6,7-epoxyheptyl? -ethylacrylate; And the like. Of these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoints of copolymerization reactivity, desirable. These epoxy group-containing unsaturated compounds having no (a2-II) alicyclic group may be used alone or in combination of two or more.

(A2) copolymer may be obtained by polymerizing (a3) an alicyclic group-containing unsaturated compound having no epoxy group together with the unsaturated carboxylic acid (a1) and the unsaturated compound containing an epoxy group (a2).

(a3) The 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 isobonyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a3) alicyclic group-containing unsaturated compounds may be used alone or in combination of two or more.

Specifically, examples of (a3) unsaturated alicyclic group-containing compounds 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 from the standpoint of easily obtaining a photosensitive resin composition having good developability, and the following formulas (a3-3) and Are more preferable.

In the formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ²² is preferably a single bond, a straight chain or branched alkylene group such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene. As R ²³ , for example, methyl group and ethyl group are preferable.

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

Examples of the (meth) acrylic esters include linear or branched (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate and t- Chain alkyl (meth) acrylates; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono Perfluoro (meth) acrylate; And the like.

The (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (Meth) acrylamide, N-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.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2- But are not limited to, ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether Alkyl vinyl ethers such as methyl vinyl ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether and vinyl anthranyl ether; And the like.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethylacetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl -? - phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl naphthoate.

Examples of the styrenes include styrene; Examples of the monomer include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, , And acetoxymethylstyrene; Alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; But are not limited to, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Styrene, and 4-fluoro-3-trifluoromethylstyrene; And the like.

The proportion of the constituent unit derived from the (a1) unsaturated carboxylic acid in the (A2) copolymer is preferably 1 to 25% by weight, and more preferably 8 to 16% by weight. The proportion of the constituent unit derived from the (a3) alicyclic group-containing unsaturated compound in the (A2) copolymer is preferably 1 to 30% by weight, more preferably 5 to 20% by weight.

The proportion of the structural unit derived from the (a2) epoxy group-containing unsaturated compound in the (A2) copolymer is preferably 20 to 60% by weight, and more preferably 20 to 40% by weight.

The weight average molecular weight (Mw: measured value by gel permeation chromatography (GPC) in terms of polystyrene conversion, which is the same in this specification) of the (A2) copolymer is preferably from 2,000 to 200,000, and more preferably from 5,000 to 30,000. When the amount is in the above range, the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easy to be obtained.

The copolymer (A2) can be produced by a known radical polymerization method. That is, they can be produced by dissolving each compound and a known radical polymerization initiator in a polymerization solvent and then heating and stirring.

The (A) alkali-soluble resin is preferably a (A3) copolymer having at least a constituent unit derived from an unsaturated carboxylic acid (a1) and a constituent unit having a polymerizable moiety between a photopolymerizable monomer (B) (A4) having at least a constituent unit derived from an unsaturated carboxylic acid (a1), a constituent unit derived from the unsaturated compound having an epoxy group (a2) and a constituent unit having a polymerizable moiety between a photopolymerizable monomer (B) Resins containing a copolymer may also be suitably used. When the alkali-soluble resin (A) includes the (A3) copolymer or the (A4) copolymer, the adhesion of the photosensitive resin composition to the substrate and the destructive strength after curing of the photosensitive resin composition can be increased.

(A3) copolymers and (A4) copolymers are copolymers of (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrene Or the like may be further copolymerized.

The constituent unit having a polymerizable moiety with the photopolymerizable monomer (B) is preferably an ethylenic unsaturated group as the polymerizable moiety (B) with the photopolymerizable monomer. The (A3) copolymer can be prepared by reacting at least a part of the carboxyl groups contained in the homopolymer of (a1) unsaturated carboxylic acid with the epoxy group-containing unsaturated compound (a2). The copolymer (A4) is obtained by copolymerizing at least a part of the epoxy group in the copolymer having the constituent unit derived from the (a1) unsaturated carboxylic acid and the constituent unit derived from the unsaturated compound containing the epoxy group (a2) And then reacting it with a carboxylic acid.

The weight average molecular weight of the (A3) copolymer and the (A4) copolymer is preferably from 2,000 to 50,000, and more preferably from 5,000 to 30,000. When the amount is in the above range, the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easy to be obtained.

The content of the alkali-soluble resin (A) is preferably 30 to 90% by weight, more preferably 45 to 75% by weight, based on the solid content of the photosensitive resin composition. When the amount is in the above range, balance of developability tends to be easily obtained.

The constituent unit having a polymerizable moiety with the photopolymerizable monomer (B) is preferably an ethylenic unsaturated group as the polymerizable moiety (B) with the photopolymerizable monomer. The copolymer (A2) is obtained by reacting a part of the epoxy group in the copolymer having the constituent unit derived from the (a1) unsaturated carboxylic acid and the constituent unit derived from the unsaturated compound containing the epoxy group (a2) with the unsaturated carboxylic acid (a1) Can be prepared.

The weight average molecular weight of the copolymer (A2) is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. Within the above range, there is a tendency that the film forming ability of the photosensitive resin composition and the balance of developability after exposure tends to be easily achieved.

The content of the alkali-soluble resin (A) is preferably 30 to 90% by weight, more preferably 45 to 75% by weight, based on the solid content of the photosensitive resin composition. When the amount is in the above range, balance of developability tends to be easily obtained.

&Lt; (B) Photopolymerizable monomer &gt;

As the photopolymerizable monomer (B) contained in the photosensitive resin composition according to the present invention, a monomer having an ethylenic unsaturated group can be preferably used. Monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy Acrylates such as methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl acrylate, Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, (Meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (Meth) acrylate of 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and phthalic acid derivatives . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include 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, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol 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, dipentaerythritol (Meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene di (Meth) acrylamide, (meth) acrylamide methylene ether, a condensation product of a polyhydric alcohol and N-methylol (meth) acrylamide, and a reaction product of 2-hydroxyethyl mother And the like can be meona, triacrylate formal. These polyfunctional monomers may be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, a multifunctional monomer having three or more functional groups is preferable, and a multifunctional monomer having six or more functional groups is more preferable because the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition can be enhanced .

The content of the component (B) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, based on the solid content of the photosensitive resin composition. When the concentration is in the above range, a balance between sensitivity, developability and resolution tends to be easily obtained.

<(C) Photopolymerization initiator>

The photopolymerization initiator (C) contained in the photosensitive resin composition according to the present invention is not particularly limited, and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2- hydroxyethoxy) 2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone, (9-ethyl-6-nitro-9H-carbazol-3-yl) 1- [4- (2-methoxy-1-methylethoxy) -2-methylphenyl] methanone O- Acetyl oxime, (O-benzoyloxime)], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, Dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl- beta -methoxyethyl acetal, benzyldimethyl Ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- 4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, Benzoyl peroxide, cumene peroxide, 2-ethylhexanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, Mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazole dimer, benzo Phenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4 ' -Bisdiethylaminobenzophenone, 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, P-tert-butylacetophenone, p-tert-butyldichloroacetophenone,?,? -Dichloro-4-phenoxyacetophenone, p- Phenylacetone, 1,7-bis- (9-phenylacetone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl- Acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, Tris (Tree (Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4, (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [ (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis 4-methoxyphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4- methoxy) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl- - (2-bromo-4-methoxy) styryl Phenyl-s-triazine, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity. Especially preferred among the oxime-based photopolymerization initiators are ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] 1- (O- 1- (9-ethyl-6- (pyrrol-2-ylcarbonyl) -9H-carbazol-3-yl] (Phenylthio) -, 2- (O-benzoyloxime)].

The content of the component (C) is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, based on the solid content of the photosensitive resin composition. When the content of the component (C) is within the above range, a photosensitive resin composition capable of forming a pattern having excellent water resistance can be obtained.

Further, the photoinitiator may be combined with the component (C). Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, Dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 9,10- dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, Diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 2-mercaptobenzoimidazole, 2-mercapto-5- Thiol compounds such as methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiators may be used alone or in combination of two or more.

&Lt; (D) Silane coupling agent &gt;

The photosensitive resin composition according to the present invention includes a silane coupling agent represented by the following formula (1). Thus, by using the photosensitive resin composition according to the present invention, it is possible to form a pattern having good adhesion to a substrate and good water resistance. The photosensitive resin composition may contain two or more kinds of silane coupling agents represented by the formula (1) in combination.

R ¹ _m R ² _(3-m) Si-R ³ -NH-C (O) -YR ⁴ -X (One)

(In the formula (1), R ¹ is an alkoxy group, R ² is an alkyl group, m is an integer of 1 to 3, R ³ is an alkylene group, Y is -NH-, -O- or -S- , R ⁴ is a single bond or an alkylene group, X is a nitrogen heteroaryl group which may have a substituent or may be a monocyclic or polycyclic ring, a ring bonding with -YR ⁴ - in X is a nitrogen-containing six- ⁴ - is bonded to a carbon atom in the nitrogen-containing six-membered aromatic ring.

In the formula (1), R ¹ is an alkoxy group. The number of carbon atoms of the alkoxy group relative to R ¹ is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2 in view of the reactivity of the silane coupling agent (D). Specific preferred examples of R ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, Hexyloxy group. Of these alkoxy groups, a methoxy group and an ethoxy group are preferable.

The silanol group formed by the hydrolysis of the alkoxy group R ¹ reacts with the surface of the substrate or the like to improve the adhesion of the pattern formed by using the photosensitive resin composition to the substrate surface. Therefore, it is preferable that m is 3 in view of easiness of improving the adhesion of the pattern to the substrate surface.

In the formula (1), R ² is an alkyl group. As to R ² , the number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 or 2 in view of the reactivity of the silane coupling agent (D). Specific preferred examples of R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.

In the formula (1), R ³ is an alkylene group. The number of carbon atoms of the alkylene group relative to R ³ is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 2 to 4. Specific preferred examples of R ³ include a methylene group, a 1,2-ethylene group, a 1,1-ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, Butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane- Diyl group, a butane-2,3-diyl group, a pentane-1,5-diyl group, a pentane-1,4-diyl group and a hexane-1,6-diyl group, A nonyl-1,9-diyl group, a decan-1,10-diyl group, an undecane-1,11-diyl group and a dodecane-1,12-diyl group. Of these alkylene groups, a 1,2-ethylene group, a propane-1,3-diyl group and a butane-1,4-diyl group are preferable.

Y is preferably -NH-, -O- or -S-, and is preferably -NH-. (D) as a silane coupling agent because a bond represented by -CO-NH- is lower than a bond represented by -CO-O- or -CO-S- because Y is -NH- because the bond is more difficult to hydrolyze When a photosensitive resin composition is used, it is easy to form a pattern having excellent water resistance.

R ⁴ is a single bond or an alkylene group, preferably a single bond. A preferable example of the case where R ⁴ is an alkylene group is the same as R ³ .

X is a nitrogen-containing heteroaryl group which may have a substituent, may be monocyclic or polycyclic, a ring bonding with -YR ⁴ - in X is a nitrogen-containing 6-membered aromatic ring, and -YR ⁴ - Carbon atoms. Although the reason is not clear, when a photosensitive resin composition comprising the compound (X) having X as a silane coupling agent is used, a pattern excellent in adhesion to a substrate and water resistance can be formed.

When X is a polycyclic heteroaryl group, the heteroaryl group may be a group condensed with a plurality of monocyclic rings, or a plurality of monocyclic rings may be bonded through a single bond. When X is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 to 3. When X is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing six-membered aromatic ring in X may or may not contain a heteroatom, and may not be an aromatic ring or an aromatic ring.

Examples of the substituent which X as the nitrogen-containing heteroaryl group may have include 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, an alkenyl group having 2 to 6 carbon atoms A nitro group, a nitro group, an amino group, a hydroxyl group, a mercapto group, a cyano group, a sulfonic acid group, a carboxyl group and a halogen atom. The number of substituents of X is not particularly limited as long as it does not impair the object of the present invention. The number of substituents of X is preferably 5 or less, more preferably 3 or less. When X has a plurality of substituents, the plurality of substituents may be the same or different.

Preferable examples of X include groups represented by the following formulas.

Among these formulas, the group of the following formula is more preferable as X.

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

The content of the component (D) is preferably 0.2 to 10% by weight, more preferably 0.5 to 7% by weight, based on the solid content of the photosensitive resin composition, excluding the coloring agent. By setting the content of the component (D) in the above range, it is easy to form a pattern excellent in adhesion to a substrate and water resistance by using a photosensitive resin composition.

<(E) Colorant>

The photosensitive resin composition according to the present invention may further contain (E) a colorant.

The colorant (E) contained in the photosensitive resin composition according to the present invention is not particularly limited. For example, a color index (CI) (published by The Society of Dyers and Colourists) is classified into pigments It is preferable to use a compound having a color index (CI) number as described below.

Examples of suitable yellow pigments include C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, .

Examples of suitable orange pigments include C.I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the numbers are described), 5,13,14,16,17,24,34,36,38,40,43,46,49,51 , 55, 59, 61, 63, 64, 71, and 73, respectively.

Examples of suitable purple pigments include C.I. Pigment Violet 1 (hereinafter, the same is true of C. I. Pigment Violet), and only the numbers are listed. 19, 23, 29, 30, 32, 36, 37, 38, 39, 40,

Examples of suitable red pigments include C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same and only the numbers are described below), 2,3,4,5,6,7,8,9,10,11,12,14,15,16 48: 3, 48: 4, 49: 1, 49: 1, 48, : 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: : 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217 , 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264 and 265.

Examples of suitable blue pigments include C.I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only the numbers are listed), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, .

Examples of the pigments of the other colors that can be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Pigment Black 7 and the like.

When a colorant is used as the light shielding agent, it is preferable to use a black pigment or a purple pigment as the light shielding agent. Examples of the black pigments and violet pigments include metal oxides, complex oxides, metal sulfides, metal sulfates or metal carbonates such as carbon black, perylene pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, Etc., organic substances, and inorganic substances. Among these, it is preferable to use carbon black having high light shielding properties.

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

As the light-shielding agent, a perylene pigment is also preferable. Specific examples of the perylene pigments include perylene pigments represented by the following formula (e-1), perylene pigments represented by the following formula (e-2) and perylene pigments represented by the following formula (e-3) have. As commercial products, products such as K0084 and K0086 manufactured by BASF, or Pigment Black 21, 30, 31, 32, 33 and 34 may be suitably used as a perylene pigment.

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

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

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

Examples of 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 described in JP 62-1753 A, , And the like. That is, a heating reaction is conducted in water or an organic solvent using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials. Then, the obtained preparation is re-precipitated in sulfuric acid or recrystallized in water, an organic solvent or a mixed solvent thereof to obtain the desired product.

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

The light-shielding agent may contain pigments of hue such as red, blue, green, and sulfur together with the above-mentioned black pigment or purple pigment for the purpose of preparing a color tone. The color pigment other than the black pigment or the purple pigment can be appropriately selected from known pigments. For example, as the pigment of a color other than a black pigment or a purple pigment, the above-mentioned various pigments can be used. The amount of the coloring matter of a different color other than the black pigment or the violet pigment is preferably 15% by weight or less, more preferably 10% by weight or less based on the total weight of the light-shielding agent.

In order to uniformly disperse the colorant in the photosensitive resin composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of polyethylene imine type, urethane resin type or acrylic resin type. Particularly, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

The inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used in combination, the organic pigments are preferably used in an amount of 10 to 80 parts by weight based on 100 parts by weight of the total of the inorganic pigments and the organic pigments, And more preferably 20 to 40 parts by weight.

The amount of the coloring agent to be used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention. Typically, the amount is preferably 5 to 70 parts by weight, more preferably 25 to 60 parts by weight per 100 parts by weight of the total solid content of the photosensitive resin composition The weight part is more preferable.

The colorant is preferably added to the photosensitive resin composition after preparing a dispersion in which the colorant is dispersed at a suitable concentration using a dispersant.

<(S) Organic solvents>

The photosensitive resin composition according to the present invention preferably contains (S) an organic solvent (hereinafter also referred to as "(S) component") for improving the applicability and adjusting the viscosity.

Specific examples of the organic solvent 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, 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- 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, (Poly) alkylene glycols such as glycol monomethyl ether, tripropylene glycol monoethyl ether and the like Call monomethyl ether; (Propylene glycol monomethyl ether acetate), 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 (PGMEA) Alkylene glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, Propyl acetate, n-butyl acetate, n-butyl butyrate, n-butyl butyrate, n-butyl acetate, i-pentyl acetate, n-butyl acetate, Other esters such as methyl, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide; And the like. Of these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, the above-mentioned other ethers, alkyl lactates, and other esters described above are preferable, and alkylene glycol monoalkyl ether acetates, Other ethers, and the above-mentioned other esters are more preferable. These solvents may be used alone or in combination of two or more.

The content of the component (S) is not particularly limited and is suitably set according to the applied thin film at a concentration applicable to a substrate or the like. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and even more preferably 20 to 30 cp. The solid concentration is preferably 5 to 100% by weight, more preferably 20 to 50% by weight.

<Other ingredients>

The photosensitive resin composition according to the present invention may contain an additive such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and a defoaming agent, if necessary. Any additive may be any conventionally known one. Examples of the surfactant include anionic, cationic and nonionic surfactants. Examples of the adhesion improver include conventionally known silane coupling agents. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monoethyl ether and the like Examples of the antifoaming agent include silicon compounds and fluorine compounds.

&Lt; Preparation method of photosensitive resin composition >

The photosensitive resin composition according to the present invention can be prepared by mixing (dispersing and kneading) each of the above components with a stirrer such as a three-stage roll mill, a ball mill, a sand mill or the like, and filtering with a filter such as a 5 占 퐉 membrane filter as necessary.

«Pattern formation method»

In order to form a pattern using the photosensitive resin composition of the present invention, first, a non-contact type coating device such as a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater, a spinner (rotary coating device), a curtain flow coater, The resin composition is coated on a substrate to form a coating film.

Subsequently, the coating film is dried as required. The drying method is not particularly limited and includes, for example, (1) a method of drying on a hot plate at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, (2) (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several minutes to several hours, and the like.

Subsequently, an active energy ray such as an infrared ray, an excimer laser beam or the like is irradiated through a negative type mask to expose the coated film on the substrate in a position-selective manner. The energy dose to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably about 30 to 2000 mJ / cm ² , for example.

A pattern of a desired shape is formed by developing the positionally selectively exposed film with a developing solution. 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 developer include organic ones such as monoethanolamine, diethanolamine and triethanolamine; and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Subsequently, post-baking is preferably performed at about 200 ° C to 250 ° C with respect to the pattern of the developer.

The pattern formed by the above-described method using the photosensitive resin composition of the present invention is suitably used for various purposes because of its excellent adhesion to substrates and water resistance. Particularly, in a black matrix provided in various display devices typified by a liquid crystal display device, it is strongly required that the black matrix has excellent adhesion to a substrate and water resistance from the viewpoint of reliability of a product. Accordingly, in the photosensitive resin composition according to the present invention, a pattern formed using a photosensitive resin composition containing a colorant containing a light-shielding agent is suitably used as a black matrix.

[ Example ]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Example]

In the examples, the following compounds 1 to 8 were used as silane coupling agents. In the comparative examples, the following compounds 9 to 17 were used as silane coupling agents.

In Examples 1 to 10 and Comparative Examples 1 to 9, a resin (A-1) synthesized by the method described below as an alkali-soluble resin was used.

First, 235 g of bisphenol fluorene 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 were prepared in a 500 ml four- At a rate of 25 ml / min while blowing air. Subsequently, the solution was gradually elevated to a cloudy state and heated to 120 DEG C to be completely dissolved. At this time, the solution became gradually transparent dots, but stirring was continued. During this period, the acid value was measured, and heating and stirring were continued until the concentration was less than 1.0 mg KOH / g. It took 12 hours until the acid value reached the target value. Then, the mixture was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula (a-4) which was colorless and transparent and was in a solid state.

Subsequently, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and slowly heated to 110 Lt; RTI ID = 0.0 &gt; 115 C &lt; / RTI &gt; After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum. The resin (A-1) corresponds to the resin represented by the formula (a-1).

In Examples 11 to 18 and Comparative Examples 10 to 18, a resin (A-2) composed of the following units I to III shown below was used as an alkali-soluble resin. In the following formulas, the lower right figure of each unit means the content (% by weight) of each unit in Resin (A-2). The weight average molecular weight of Resin (A-2) was 7000.

In the Examples and Comparative Examples, dipentaerythritol hexaacrylate (DPHA) was used as a photopolymerizable monomer.

In Examples and Comparative Examples, a photopolymerization initiator represented by the following formula was used.

In Examples 1 to 8 and Comparative Examples 1 to 9, a carbon black dispersion (CF black (manufactured by Mikuni Shikiso Co., Ltd., solid content concentration of 25% by weight) in which carbon black was dispersed in 3-methoxybutyl acetate was used.

[Examples 1 to 8 and Comparative Examples 1 to 9]

100 parts by weight of an alkali-soluble resin (resin (A-1)), 35 parts by weight of a photopolymerizable monomer (DPHA), 15 parts by weight of a photopolymerization initiator, 3 parts by weight of a silane coupling agent of the kind shown in Table 1, And 500 parts by weight of the dispersion were mixed, and the mixture was diluted with an organic solvent to a solid concentration of 15% by weight to obtain a photosensitive resin composition. As the organic solvent used for diluting the mixture, 3-methoxybutyl acetate (MA), propylene glycol monomethyl ether acetate (PM) and cyclohexanone (AN) were mixed at a MA / PM / AN = ) Were used. The obtained photosensitive resin composition was evaluated in terms of fine line adhesion and water resistance by the following methods.

(Evaluation of fine wire adhesion)

The photosensitive resin composition was coated on a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 90 캜 for 120 seconds to form a coating film having a thickness of 1.0 탆. Subsequently, the coating film was irradiated with ultraviolet rays using a Miller Projection aligner (trade name: TME-150RTO, manufactured by Topcon Co., Ltd.) through a negative mask having an exposure gap of 50 占 퐉 and a pattern with a width of 5 占 퐉. The exposure was performed in four steps of 10, 20, 40 and 100 mJ / cm ² . After the exposure, the coated film was developed with a 0.04 wt% KOH aqueous solution at 26 DEG C for 50 seconds, and post-baked at 230 DEG C for 30 minutes to form a line pattern.

The line pattern formed at each exposure amount was observed by an optical microscope to evaluate the fine line adhesion. &Quot; Good &quot; was determined when no peeling from the substrate was observed in the formed pattern. &Quot; Bad &quot; was determined when a part or all of the formed pattern could not be separated from the substrate to form a pattern of a desired shape. Determination of the fine line adhesion of the photosensitive resin compositions of each of the Examples and Comparative Examples is shown in Table 1 for each exposure amount.

(Water resistance evaluation)

A coating film having a film thickness of 1.0 mu m was formed on a glass substrate in the same manner as in the evaluation of fine wire adhesion. The formed coating film was exposed to light at an exposure dose of 100 mJ / cm ² without interposing a mask to form a cured film on the glass substrate. And the water resistance was evaluated using the cured film formed. The glass substrate having the cured film was placed in a pressure-resistant container for 24 hours under the atmosphere of 120 캜, 2 atmospheric pressure, and 100% humidity. At the time points of 2 hours, 6 hours, 12 hours and 24 hours, the glass substrate was taken out from the pressure-resistant container, and the presence or absence of peeling of the cured film from the glass substrate was observed. And the case where peeling of the cured film from the glass substrate was not observed was judged as &quot; good &quot;. The case where peeling of the cured film from the glass substrate was observed was judged as &quot; defective &quot;.

Silane
Coupling agent
Kinds Fine wire adhesion 10
mJ / cm ² 20
mJ / cm ² 40
mJ / cm ² 100
mJ / cm ² Example 1 Compound 1 Good Good Good Good Example 2 Compound 2 Good Good Good Good Example 3 Compound 3 Good Good Good Good Example 4 Compound 4 Good Good Good Good Example 5 Compound 5 Good Good Good Good Example 6 Compound 6 Good Good Good Good Example 7 Compound 7 Good Good Good Good Example 8 Compound 8 Good Good Good Good Comparative Example 1 Compound 9 Bad Bad Bad Bad Comparative Example 2 Compound 10 Good Good Good Good Comparative Example 3 Compound 11 Bad Bad Bad Bad Comparative Example 4 Compound 12 Good Good Good Good Comparative Example 5 Compound 13 Bad Bad Good Good Comparative Example 6 Compound 14 Bad Bad Bad Good Comparative Example 7 Compound 15 Bad Bad Good Good Comparative Example 8 Compound 16 Bad Bad Bad Good Comparative Example 9 Compound 17 Bad Bad Bad Good

Silane
Coupling agent
Kinds Water resistance 2 hours
6 hours 12 hours 24 hours Example 1 Compound 1 Good Good Good Good Example 2 Compound 2 Good Good Good Good Example 3 Compound 3 Good Good Good Good Example 4 Compound 4 Good Good Good Good Example 5 Compound 5 Good Good Good Good Example 6 Compound 6 Good Good Good Good Example 7 Compound 7 Good Good Good Good Example 8 Compound 8 Good Good Good Good Comparative Example 1 Compound 9 Good Good Good Good Comparative Example 2 Compound 10 Good Bad Bad Bad Comparative Example 3 Compound 11 Bad Bad Bad Bad Comparative Example 4 Compound 12 Good Bad Bad Bad Comparative Example 5 Compound 13 Bad Bad Bad Bad Comparative Example 6 Compound 14 Good Good Good Good Comparative Example 7 Compound 15 Good Good Good Good Comparative Example 8 Compound 16 Good Good Good Good Comparative Example 9 Compound 17 Good Good Good Bad

[Examples 9 and 10]

A photosensitive resin composition was obtained in the same manner as in Examples 2 and 4 except that the carbon black dispersion was changed to a dispersion of perylene pigment (solid content: 20% by weight, solvent: 3-methoxybutyl acetate) having the following structure. Using the obtained photosensitive resin composition, the fine line adhesion and the water resistance were evaluated in the same manner as in Examples 2 and 4. Determination of fine wire adhesion and determination of water resistance are shown in Table 3. &lt; tb &gt; &lt; TABLE &gt;

Silane
Coupling agent
Kinds Fine wire adhesion 10
mJ / cm ² 20
mJ / cm ² 40
mJ / cm ² 100
mJ / cm ² Example 9 Compound 2 Good Good Good Good Example 10 Compound 4 Good Good Good Good

Silane
Coupling agent
Kinds Water resistance 2 hours
6 hours 12 hours 24 hours Example 9 Compound 2 Good Good Good Good Example 10 Compound 4 Good Good Good Good

From the Tables 1 to 3, it was confirmed that the photosensitive resin composition of the embodiment containing the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator and the colorant as the silane coupling agent and the compound represented by the formula (1) It can be seen that both the adhesion to a substrate of a good pattern and the good water resistance can be achieved.

On the other hand, from Table 1 and Table 2, it can be seen that the photosensitive resin composition of the comparative example which contains the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator and the colorant but does not contain the compound represented by the formula (1) It can be seen that the pattern formed by using the resist pattern can not satisfy the adhesion to the substrate of a good pattern and the good water resistance.

Particularly, according to Comparative Examples 6 to 8, when the heterocyclic ring is a nitrogen-containing five-membered ring directly bonded to the -NH-CO-NH- group with respect to the silane coupling agent contained in the photosensitive resin composition, It can be seen that the pattern is poor in thin wire adhesion even when water resistance is excellent.

Further, according to Comparative Example 9, when the benzene ring is directly bonded to the -NH-CO-NH- group with respect to the silane coupling agent contained in the photosensitive resin composition, the pattern formed using the photosensitive resin composition has poor thin wire adhesion, The water resistance is slightly lowered.

[Examples 11 to 18 and Comparative Examples 10 to 18]

58.5 parts by weight of an alkali-soluble resin (resin (A-2)), 40 parts by weight of a photopolymerizable monomer (DPHA), 1.5 parts by weight of a photopolymerization initiator and 3 parts by weight of a silane coupling agent of the kind shown in Table 2, Was diluted with an organic solvent to a solid concentration of 15% by weight to obtain a photosensitive resin composition. A mixed solvent in which diethylene glycol methyl ethyl ether (MEDG) and propylene glycol monomethyl ether acetate (PM) were mixed at MEDG / PM = 60/40 / (weight ratio) was used as an organic solvent used for diluting the mixture. The obtained photosensitive resin composition was evaluated in the same manner as in Example 1 for its fine line adhesion and water resistance.

Silane
Coupling agent
Kinds Fine wire adhesion 10
mJ / cm ² 20
mJ / cm ² 40
mJ / cm ² 100
mJ / cm ² Example 11 Compound 1 Good Good Good Good Example 12 Compound 2 Good Good Good Good Example 13 Compound 3 Good Good Good Good Example 14 Compound 4 Good Good Good Good Example 15 Compound 5 Good Good Good Good Example 16 Compound 6 Good Good Good Good Example 17 Compound 7 Good Good Good Good Example 18 Compound 8 Good Good Good Good Comparative Example 10 Compound 9 Bad Bad Bad Bad Comparative Example 11 Compound 10 Good Good Good Good Comparative Example 12 Compound 11 Bad Bad Bad Good Comparative Example 13 Compound 12 Bad Good Good Good Comparative Example 14 Compound 13 Bad Bad Good Good Comparative Example 15 Compound 14 Bad Bad Bad Good Comparative Example 16 Compound 15 Bad Bad Good Good Comparative Example 17 Compound 16 Bad Bad Bad Good Comparative Example 18 Compound 17 Bad Bad Bad Good

Silane
Coupling agent
Kinds Water resistance 2 hours
6 hours 12 hours 24 hours Example 11 Compound 1 Good Good Good Good Example 12 Compound 2 Good Good Good Good Example 13 Compound 3 Good Good Good Good Example 14 Compound 4 Good Good Good Good Example 15 Compound 5 Good Good Good Good Example 16 Compound 6 Good Good Good Good Example 17 Compound 7 Good Good Good Good Example 18 Compound 8 Good Good Good Good Comparative Example 10 Compound 9 Good Good Good Good Comparative Example 11 Compound 10 Good Bad Bad Bad Comparative Example 12 Compound 11 Good Bad Bad Bad Comparative Example 13 Compound 12 Good Good Bad Bad Comparative Example 14 Compound 13 Bad Bad Bad Bad Comparative Example 15 Compound 14 Good Good Good Good Comparative Example 16 Compound 15 Good Good Good Good Comparative Example 17 Compound 16 Good Good Good Good Comparative Example 18 Compound 17 Good Good Good Good

From Table 5 and Table 6, it can be seen that a pattern formed using the photosensitive resin composition of the Example containing the alkali-soluble resin, the photopolymerizable monomer, and the photopolymerization initiator and containing the compound represented by the formula (1) described above as the silane coupling agent It can be seen that both the adhesion to a substrate of a good pattern and the good water resistance can be achieved.

On the other hand, it can be seen from Tables 5 and 6 that the photosensitive resin composition of the comparative example which contains the alkali-soluble resin, the photopolymerizable monomer and the photopolymerization initiator but does not contain the compound represented by the above-mentioned formula (1) It can be seen that the pattern formed can not satisfy the adhesion to the substrate of a good pattern and the good water resistance.

Particularly, according to Comparative Examples 15 to 18, when the ring is a nitrogen-containing 5-membered ring directly bonded to the -NH-CO-NH- group with respect to the silane coupling agent contained in the photosensitive resin composition or a benzene ring, It can be seen that the pattern is poor in thin wire adhesion even when water resistance is excellent.

Claims (6)

(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent,
Wherein the silane coupling agent (D) is a compound represented by the following formula (1):
R ¹ _m R ² _(3-m) Si-R ³ -NH-C (O) -YR ⁴ -X (One)
(In the formula (1), R ¹ is an alkoxy group, R ² is an alkyl group, m is an integer of 1 to 3, R ³ is an alkylene group, Y is -NH-, -O- or -S- , R ⁴ is a single bond or an alkylene group, X is a nitrogen heteroaryl group which may have a substituent or may be a monocyclic or polycyclic ring, a ring bonding with -YR ⁴ - in X is a nitrogen-containing six- ⁴ - is bonded to the carbon atom in the nitrogen-containing six-membered aromatic ring. The method according to claim 1,
(E) a colorant. The method of claim 2,
Wherein the coloring agent (E) is a light-shielding agent. A step of applying the photosensitive resin composition described in any one of claims 1 to 3 on a substrate to form a coating film;
Selectively exposing the coating film to light;
And developing the exposed coating film. A black matrix formed by using the photosensitive resin composition according to claim 3. A display device comprising the black matrix according to claim 5.