KR102341048B1 - Photosensitive resin composition - Google Patents

Abstract

[assignment]
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 photosensitive resin composition comprising a light blocking agent as a colorant in the photosensitive resin composition Black formed using To provide a display device including a matrix and the black matrix.
[Solution]
The (D) silane coupling agent of a specific structure is mix|blended with the photosensitive resin composition containing (A) alkylily-soluble resin, (B) a photopolymerizable monomer, and (C) a photoinitiator.

Description

Photosensitive resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention provides a photosensitive resin composition, a pattern forming method using the photosensitive resin composition, a black matrix formed using a photosensitive resin composition including a light blocking agent as a colorant in the photosensitive resin composition, and a display device including the black matrix is about

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

As a photosensitive resin composition used for such a use, the photosensitive resin composition containing alkali-soluble resin of a specific structure, a photoinitiator, a photopolymerizable monomer, and a coloring agent is known, for example (patent document 1).

Japanese Patent Laid-Open No. 2006-079064

For a pattern formed using the photosensitive resin composition used in electrical and electronic devices typified by display devices, for the purpose of improving the reliability of device operation, adhesion to the substrate or water resistance that can withstand use under high temperature and high humidity conditions is improved. is being demanded Although the pattern formed using the photosensitive resin composition of patent document 1 is excellent to some extent with respect to the adhesiveness to a board|substrate, and water resistance, the further improvement is calculated|required with respect to these characteristics.

The present invention has been made in view of the above problems, 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 light blocking agent as a colorant in the photosensitive resin composition An object of the present invention is to provide a black matrix formed using a photosensitive resin comprising: and a display device including the black matrix.

The present inventors repeated intensive research in order to solve the above problems. As a result, (A) alkali-soluble resin, (B) photopolymerizable monomer, and (C) photosensitive resin composition containing a photoinitiator, by mix|blending (D) a silane coupling agent of a specific structure discovered that the said subject could be solved and completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photoinitiator, and (D) a silane coupling agent,

(D) A silane coupling agent is the photosensitive resin composition which is a compound represented by following formula (1).

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

(in 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-containing heteroaryl group which may have a substituent or may be monocyclic or polycyclic, ^{the ring bonded to -YR 4} - in X is a nitrogen-containing 6-membered aromatic ring, -YR ⁴ - is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring.)

A second aspect of the present invention comprises a step of applying the photosensitive resin composition according to the first aspect on a substrate to form a coating film;

a step of positionally selectively exposing the coating film;

It is a pattern formation method including the process of developing the exposed coating film.

A 3rd aspect of this invention is a black matrix formed using the photosensitive resin composition which contains the light-shielding agent as a coloring agent among the photosensitive resin compositions which concern on 1st aspect.

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

According to the present invention, 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 photosensitive resin composition comprising a light blocking agent as a colorant in the photosensitive resin composition It is possible to provide a black matrix formed by using , and a display device including the black matrix.

«Photosensitive resin composition»

The photosensitive resin composition which concerns on this invention contains (A) alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photoinitiator, and (D) a silane coupling agent of a specific structure. Hereinafter, the essential or arbitrary components which the photosensitive resin composition which concerns on this invention contain are demonstrated in order.

<(A) alkali-soluble resin>

(A) Alkali-soluble resin (hereinafter also referred to as “component (A)”) is a resin film having a thickness of 1 μm on a substrate by using a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20 wt%. It means that the film thickness is 0.01 µm or more when immersed in a KOH aqueous solution having a concentration of 0.05 wt% for 1 minute.

(A) Alkali-soluble resin will not be specifically limited if it is resin which shows the alkali solubility mentioned above, It can select suitably from conventionally well-known resin, and can be used. (A) Resin which has a cardo structure is mentioned as resin suitable as alkali-soluble resin (A1).

(A1) It does not specifically limit as resin which has a cardo structure, Conventionally well-known resin can be used. Especially, resin represented by a 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 formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a is a single bond Or group represented by the following formula (a-3) is shown.

In addition, in the formula (a-1), Y ^a represents a residue obtained by removing 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-endo-methylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride , and glutaric anhydride.

In addition, in said Formula (a-1), Z ^a represents the residue which removed two acid anhydride groups from tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracarboxylic dianhydride.

In addition, in said Formula (a-1), m represents the integer of 0-20.

(A1) It is preferable that it is 1000-40000, and, as for the weight average molecular weight of resin which has cardo structure, it is more preferable that it is 2000-30000. By setting it as the said range, sufficient heat resistance and film strength can be acquired, obtaining favorable developability.

(A) As alkali-soluble resin, the copolymer of (a1) unsaturated carboxylic acid and the other copolymerization component of unsaturated carboxylic acid can also be used. Among these resins, a (A2) copolymer obtained by polymerizing at least (a1) an unsaturated carboxylic acid and (a2) an unsaturated compound containing an epoxy group is mentioned in that it is easy to obtain a photosensitive resin composition that provides a pattern excellent in breaking strength and adhesion to a substrate. can

(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. Among these, points, such as copolymerization reactivity, alkali solubility of resin obtained, and availability, (meth)acrylic acid and maleic anhydride are preferable. These (a1) unsaturated carboxylic acids can be used individually or in combination of 2 or more types.

(a2) Examples of the epoxy group-containing unsaturated compound include (a2-I) an unsaturated compound having an alicyclic epoxy group, (a2-II) an unsaturated compound not having an alicyclic epoxy group, (a2-I) having an alicyclic epoxy group Unsaturated compounds are preferred.

(a2-I) In the 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. Moreover, as a polycyclic alicyclic group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, tetracyclododecyl group, etc. are mentioned. These (a2-I) alicyclic epoxy group-containing unsaturated compounds can be used individually or in combination of 2 or more types.

Specific examples of the (a2-I) alicyclic epoxy group-containing unsaturated compound include compounds represented by the following formulas (a2-1) to (a2-16). Among these, in order to make developability suitable, the compound represented by the following formulas (a2-1) - (a2-6) is preferable, and the compound represented by the following formula (a2-1) - (a2-4) is more desirable.

In the formula, R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n is 0 to 10 represents an integer. R ¹² is preferably 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. 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} - ( Ph represents a phenylene group) is preferable.

(a2-II) Examples of the epoxy group-containing unsaturated compound having no alicyclic group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6 , (meth)acrylic acid epoxyalkyl esters such as 7-epoxyheptyl (meth)acrylate; α-alkyl acrylic acid epoxy alkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl glycidyl acrylate, α-n-butyl acrylate glycidyl, and α-ethyl acrylic acid 6,7-epoxyheptyl; and the like. Among these, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate are desirable. These (a2-II) epoxy group-containing unsaturated compounds which do not have an alicyclic group can be used individually or in combination of 2 or more types.

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

(a3) As an alicyclic group-containing unsaturated compound, if it is an unsaturated compound which has an alicyclic group, it will not specifically limit. 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, and a tetracyclododecyl group. These (a3) alicyclic group containing unsaturated compounds can be used individually or in combination of 2 or more types.

Specific 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 at the point that the photosensitive resin composition with favorable developability is easily obtained, and the following formulas (a3-3) and (a3-4) The compound shown is 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, 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. R ²³ is preferably a methyl group or an ethyl group, for example.

(A2) The 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 can be used individually or in combination of 2 or more types.

Examples of (meth)acrylic acid esters include linear or branched methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. chain alkyl (meth)acrylate; Chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate; and the like.

As (meth)acrylamides, (meth)acrylamide, N-alkyl (meth)acrylamide, N-aryl (meth)acrylamide, N,N-dialkyl (meth)acrylamide, N,N-aryl ( Meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, etc. are mentioned.

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-dimethylpropyl vinyl. 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; 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.

Vinyl esters include vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of styrene include styrene; Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene , alkyl styrenes such as acetoxymethyl styrene; Alkoxy styrene, such as methoxy styrene, 4-methoxy-3- methyl styrene, and dimethoxy styrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl halostyrenes such as styrene and 4-fluoro-3-trifluoromethylstyrene; and the like.

(A2) It is preferable that it is 1 to 25 weight%, and, as for the ratio of the structural unit derived from the said (a1) unsaturated carboxylic acid to a copolymer, it is more preferable that it is 8 to 16 weight%. Moreover, it is preferable that it is 1 to 30 weight%, and, as for the ratio of the structural unit derived from the said (a3) alicyclic group containing unsaturated compound to (A2) copolymer, it is more preferable that it is 5 to 20 weight%.

Moreover, 20 to 60 weight% is preferable and, as for the ratio of the structural unit derived from the said (a2) epoxy group containing unsaturated compound to (A2) copolymer, 20 to 40 weight% is more preferable.

(A2) The weight average molecular weight of the copolymer (Mw: a value measured in terms of polystyrene by gel permeation chromatography (GPC), the same herein) is preferably 2000 to 200000, more preferably 5000 to 30000. By setting it as said range, there exists a tendency for it easy to balance the film-forming ability of the photosensitive resin composition, and the developability after exposure.

(A2) A copolymer can be manufactured by a well-known radical polymerization method. That is, after each compound and a well-known radical polymerization initiator are melt|dissolved in a polymerization solvent, it can manufacture by heating and stirring.

Further, (A) as the alkali-soluble resin, the (A3) copolymer having at least a structural unit having a polymerizable site between the (a1) unsaturated carboxylic acid-derived structural unit and the (B) photopolymerizable monomer described later, or The structural unit derived from the above (a1) unsaturated carboxylic acid; Resin containing a copolymer can also be used suitably. (A) When alkali-soluble resin contains (A3) copolymer or (A4) copolymer, the adhesiveness to the board|substrate of the photosensitive resin composition, and the breaking strength after hardening of the photosensitive resin composition can be raised.

(A3) copolymer and (A4) copolymer are (meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, vinyl esters, and styrene What was further copolymerized, etc. may be sufficient.

(B) It is preferable that the structural unit which has a polymerization site|part with a photopolymerizable monomer has an ethylenically unsaturated group as a site|part which can superpose|polymerize with (B) a photopolymerizable monomer. (A3) The copolymer can be prepared by reacting at least a part of the carboxyl groups contained in the homopolymer of the (a1) unsaturated carboxylic acid with the (a2) epoxy group-containing unsaturated compound. Further, (A4) the copolymer has at least a part of the epoxy groups in the copolymer having a structural unit derived from the above (a1) unsaturated carboxylic acid, and a structural unit derived from the above (a2) epoxy group-containing unsaturated compound, and (a1) unsaturated It can prepare by making a carboxylic acid react.

(A3) It is preferable that it is 2000-50000, and, as for the weight average molecular weight of a copolymer and (A4) copolymer, it is more preferable that it is 5000-30000. By setting it as said range, there exists a tendency for it easy to balance the film-forming ability of the photosensitive resin composition, and the developability after exposure.

(A) It is preferable that it is 30 to 90 weight% with respect to solid content of the photosensitive resin composition, and, as for content of alkali-soluble resin, it is more preferable that it is 45 to 75 weight%. By setting it as the said range, it exists in the tendency for developability to balance easily.

(B) It is preferable that the structural unit which has a polymerization site|part with a photopolymerizable monomer has an ethylenically unsaturated group as a site|part which can superpose|polymerize with (B) a photopolymerizable monomer. The copolymer (A2) is prepared by reacting a part of the epoxy group in the copolymer having a structural unit derived from the (a1) unsaturated carboxylic acid and a structural unit derived from the (a2) epoxy group-containing unsaturated compound, and (a1) an unsaturated carboxylic acid. can be prepared.

It is preferable that it is 2000-50000, and, as for the weight average molecular weight of a copolymer (A2), it is more preferable that it is 5000-30000. By setting it as the said range, there exists a tendency for it easy to balance the film-forming ability of the photosensitive resin composition, and the developability after exposure.

(A) It is preferable that it is 30 to 90 weight% with respect to solid content of the photosensitive resin composition, and, as for content of alkali-soluble resin, it is more preferable that it is 45 to 75 weight%. By setting it as the said range, it exists in the tendency for developability to balance easily.

<(B) photopolymerizable monomer>

As (B) photopolymerizable monomer contained in the photosensitive resin composition which concerns on this invention, the monomer which has an ethylenically unsaturated group can be used preferably. As a monomer which has this ethylenically unsaturated group, there exist a monofunctional monomer and a polyfunctional monomer.

Monofunctional monomers include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, sheet Laconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acryl Rate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) ) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( and meth)acrylate and half (meth)acrylate of a phthalic acid derivative. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as the polyfunctional monomer, 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, trimethylolpropane tri (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, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acrylic Oxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol Diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl Ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. 2-hydroxyethyl (meth) acrylate reaction product, methylenebis (meth) ) polyfunctional monomers, such as acrylamide, (meth)acrylamide methylene ether, and the condensate of a polyhydric alcohol and N-methylol (meth)acrylamide, triacryl formal, etc. are mentioned. These polyfunctional monomers can be used individually or in combination of 2 or more types.

Among the monomers having an ethylenically unsaturated group, a trifunctional or higher polyfunctional monomer is preferable, and a hexafunctional or higher polyfunctional monomer is more preferable from the viewpoint of increasing the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition. .

(B) It is preferable that it is 5 to 60 weight% with respect to solid content of the photosensitive resin composition, and, as for content of a component, it is more preferable that it is 10 to 50 weight%. By setting it as the said range, it exists in the tendency for a sensitivity, developability, and resolution to balance easily.

<(C) Photoinitiator>

It does not specifically limit as (C) photoinitiator contained in the photosensitive resin composition which concerns on this invention, A conventionally well-known photoinitiator can be used.

Specifically as the photopolymerization initiator, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl-1-one [4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl],1-(O-acetyloxime), (9-ethyl-6-nitro-9H-carbazole-3 -yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 1,2-octanedione,1-[4-(phenylthio)-,2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylamino Ethyl benzoate, 4-dimethylamino butyl benzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-dimethylamino-2-isoamyl benzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1 ,2-propanedione-2-(O-ethoxycarbonyl)oxime, o-benzoyl methyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-Chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2- Ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumin peroxide, 2-mercaptobenzoimidazole, 2 -Mercaptobenzooxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazole dimer, benzophenone, 2-chlorobenzophenone , p,p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin , ben Join methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaceto Phenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloro Acetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosverone, pentyl-4-dimethylaminobenzoate, 9 -Phenylacridine, 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-(furan-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(trichloro Rhomethyl)-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-triazine, etc. are mentioned. These photoinitiators can be used individually or in combination of 2 or more types.

Among these, it is especially preferable from the point of a sensitivity to use an oxime system photoinitiator. Among the oxime-based photopolymerization initiators, particularly preferred are ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl],1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl],1-(O-acetyloxime) and 1,2-octanedione,1-[4- (phenylthio)-,2-(O-benzoyloxime)].

(C) It is preferable that it is 0.5 to 30 weight% with respect to solid content of the photosensitive resin composition, and, as for content of a component, it is more preferable that it is 1 to 20 weight%. (C) By making content of component into the said range, the photosensitive resin composition which can form the pattern excellent in water resistance can be obtained.

Moreover, you may combine a photoinitiation adjuvant with this (C)component. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methyl Thiol compounds, such as oxybenzothiazole, 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetramercaptoacetate, 3-mercaptopropionate, etc. are mentioned. These photoinitiation aids can be used individually or in combination of 2 or more types.

<(D) Silane coupling agent>

The photosensitive resin composition which concerns on this invention contains the silane coupling agent represented by following formula (1). For this reason, by using the photosensitive resin composition which concerns on this invention, the adhesiveness with respect to a board|substrate, and the favorable pattern of water resistance can be formed. The photosensitive resin composition may contain the silane coupling agent represented by Formula (1) in combination of 2 or more types.

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

(in 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-containing heteroaryl group which may have a substituent or may be monocyclic or polycyclic, ^{the ring bonded to -YR 4} - in X is a nitrogen-containing 6-membered aromatic ring, -YR ⁴ - is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring.)

In formula (1), R<^1> is an alkoxy group. 1-6 are preferable, as for the number of carbon atoms of an alkoxy group with respect to R<^1> , 1-4 are more preferable, and 1 or 2 are especially preferable from a reactive viewpoint of (D) a silane coupling agent. Preferred specific examples of R ¹ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group and n- A hexyloxy group is mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable.

^{When the silanol group produced by hydrolysis of R 1 as an} alkoxy group reacts with the surface of the substrate, the adhesion of the pattern formed using the photosensitive resin composition to the substrate surface is improved. For this reason, it is preferable that m is 3 from the point of being easy to improve the adhesiveness with respect to the board|substrate surface of a pattern.

In formula (1), R<^2> is an alkyl group. With respect to R<^2> , 1-12 are preferable, as for the number of carbon atoms of an alkyl group, 1-6 are more preferable, and 1 or 2 are especially preferable from a reactive viewpoint of (D) a silane coupling agent. Preferred specific examples of R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- A heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group are mentioned.

In Formula (1), R ³ is an alkylene group. 1-12 are preferable with respect to R<^3> and, as for carbon atom number of an alkylene group, 1-6 are more preferable, 2-4 are especially preferable. Preferred specific examples of R ³ include methylene group, 1,2-ethylene group, 1,1-ethylene group, propane-1,3-diyl group, 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. Among 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 -NH-, -O- or -S-, preferably -NH-. Since the bond represented by -CO-NH- is less susceptible to hydrolysis than the bond represented by -CO-O- or -CO-S- (D) containing a compound in which Y is -NH- as a silane coupling agent When the photosensitive resin composition is used, it is easy to form the pattern excellent in water resistance.

R ⁴ is a single bond or an alkylene group, preferably a single bond. Preferred examples when R ⁴ is an alkylene group are the same as those ^{of R 3 .}

X is a nitrogen-containing heteroaryl group which may have a substituent or may be monocyclic or polycyclic, ^{a ring bonded to -YR 4} - in X is a nitrogen-containing 6-membered aromatic ring, and -YR ⁴ - is a nitrogen-containing 6-membered aromatic ring in the group. bonds with carbon atoms. Although the reason is not clear, if the photosensitive resin composition which contains the compound which has such X as (D) a silane coupling agent is used, the pattern excellent in adhesiveness to a board|substrate and water resistance can be formed.

When X is a polycyclic heteroaryl group, the heteroaryl group may be a group in which a plurality of monocyclic rings are condensed, or a contribution in which a plurality of monocyclic rings are bonded through a single bond. When X is a polycyclic heteroaryl group, the number of rings included in the polycyclic heteroaryl group is preferably 1-3. When X is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing 6-membered aromatic ring in X may or may not contain a hetero atom, and may or may not be an aromatic ring.

As a substituent which X, which is a nitrogen-containing heteroaryl group, may 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, an alkenyl group having 2 to 6 carbon atoms and a nyloxy group, an aliphatic acyl group having 2 to 6 carbon atoms, a benzoyl group, a nitro group, a nitroso 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 which X has is not particularly limited in a range that does not impair the object of the present invention. 5 or less are preferable and, as for the number of the substituents which X has, 3 or less are more preferable. When X has a plurality of substituents, the plurality of substituents may be the same or different.

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

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

The following compounds 1-8 are mentioned as a suitable specific example of the compound represented by Formula (1) demonstrated above.

(D) It is preferable that it is 0.2 to 10 weight% with respect to solid content of the photosensitive resin composition except a coloring agent, and, as for content of a component, it is more preferable that it is 0.5 to 7 weight%. (D) By making content of a component into said range, it is easy to form the pattern excellent in the adhesiveness to a board|substrate and water resistance using the photosensitive resin composition.

<(E) Colorant>

The photosensitive resin composition which concerns on this invention may also contain the (E) coloring agent further.

Although it does not specifically limit as (E) coloring agent contained in the photosensitive resin composition which concerns on this invention, For example, in a color index (CI; issued by The Society of Dyers and Colorists), it is classified as a pigment It is preferable to use a compound with a specific color index (CI) number as shown below.

Examples of yellow pigments that can be suitably used include C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only numbers are described), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119 , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180 and 185. can

Examples of orange pigments that can be suitably used include C.I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same, and only 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.

Examples of purple pigments that can be suitably used include C.I. Pigment Violet 1 (hereinafter, "C.I. Pigment Violet" is the same, and only the numbers are described), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40 and 50 are mentioned.

Examples of red pigments that can be suitably used include C.I. Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, and only numbers are described), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 , 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49 :2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81 :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 , 170, 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 blue pigments that can be suitably used include C.I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same, and only numbers are described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64 and 66. can

Examples of pigments of different 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. Black pigments, such as Pigment Black 7, are mentioned.

Moreover, when making a colorant into a light-shielding agent, it is preferable to use a black pigment or a purple pigment as a light-shielding agent. Examples of black pigments and purple pigments include carbon black, perylene pigments, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver and other metal oxides, complex oxides, metal sulfides, metal sulfates or metal carbonates. Various pigments are mentioned regardless of an organic substance and an inorganic substance. Among these, it is preferable to use carbon black which has high light-shielding property.

As carbon black, well-known carbon blacks, such as channel black, furnace black, thermal black, and lamp black, can be used, However, It is preferable to use channel black excellent in light-shielding property. Moreover, you may use resin-coated carbon black.

Moreover, as a light-shielding agent, a perylene type pigment is also preferable. 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). have. As a commercial item, the product names K0084 and K0086 by BASF Corporation, Pigment Black 21, 30, 31, 32, 33, 34, etc. can be used conveniently as a perylene type pigment.

In formula (e-1), R ^e1 and ^Re2 each independently represent an alkylene group having 1 to 3 ^{hydrogen atoms, and Re3} 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 formula (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom or a C1-C22 alkyl group, and may contain the hetero atom of N, O, S or P. When R ^e7 and R ^e8 are an alkyl group, the alkyl group may be linear or branched.

The compound represented by the formula (e-1), the compound represented by the formula (e-2), and the compound represented by the formula (e-3) are, for example, Japanese Patent Application Laid-Open Nos. 62-1753 and 63-26784 It can be synthesized using the method described in That is, using perylene-3,5,9,10-tetracarboxylic acid or its dianhydride and amines as raw materials, the heating reaction is performed in water or an organic solvent. Then, the target product can be obtained by recrystallizing the obtained preparation in sulfuric acid or recrystallizing it in water, an organic solvent, or a mixed solvent thereof.

In order to disperse|distribute a perylene-type pigment favorably in the photosensitive resin composition, it is preferable that the average particle diameter of a perylene-type pigment is 10-1000 nm.

The light-shielding agent may contain pigment|dye of hues, such as red, blue, green, and yellow, with the said black pigment and a purple pigment for the objective of color tone preparation, etc. The pigment|dye of a color other than a black pigment and a purple pigment can be suitably selected from well-known pigment|dye. For example, as a pigment|dye of color other than a black pigment or a purple pigment, the said various pigment can be used. 15 weight% or less is preferable with respect to the total weight of the light-shielding agent, and, as for the usage-amount of pigments other than a black pigment or purple pigment, 10 weight% or less is more preferable.

In order to disperse|distribute said coloring agent uniformly in the photosensitive resin composition, you may use a dispersing agent further. As such a dispersing agent, it is preferable to use a polyethyleneimine type, a urethane resin type, and an acrylic resin type polymer dispersing agent. In particular, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

In addition, the inorganic pigment and the organic pigment may be used alone or in combination of two or more, respectively, but when used in combination, it is preferable to use the organic pigment in an amount of 10 to 80 parts by weight with respect to 100 parts by weight of the total amount of the inorganic pigment and the organic pigment, It is more preferable to use in the range of 20-40 weight part.

The usage-amount of the coloring agent in the photosensitive resin composition can be suitably selected within the range which does not impair the objective of this invention, Typically, 5-70 weight part is preferable with respect to a total of 100 weight part of solid content of the photosensitive resin composition, and 25-60 A weight part is more preferable.

It is preferable to add a coloring agent to the photosensitive resin composition, after making it into the dispersion liquid disperse|distributed to the appropriate density|concentration using a dispersing agent.

<(S) organic solvent>

It is preferable that the photosensitive resin composition which concerns on this invention contains the (S) organic solvent (henceforth "(S) component") for the improvement of applicability|paintability, and viscosity adjustment.

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- 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 (poly)alkylene glycol monoalkyl ethers such as glycol monomethyl ether and tripropylene glycol monoethyl ether; (polyethylene 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), 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, 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; 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethoxy ethyl acetate, ethyl hydroxyacetate, 2 -Hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 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-propyl butyrate, i-propyl butyrate, n-butyl butyrate, pyrbic acid other esters such as methyl, ethyl pyrivate, n-propyl pyrivate, 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. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers, lactic acid alkyl esters, and other esters described above are preferable. Other ethers and the above-mentioned other esters are more preferable. These solvents can be used individually or in combination of 2 or more types.

(S) Content of a component is not specifically limited, It sets suitably according to the coating thin film at the density|concentration which can be apply|coated to a board|substrate etc. It is preferable that it is 5-500cp, and, as for the viscosity of the photosensitive resin composition, it is more preferable that it is 10-50cp, It is more preferable that it is 20-30cp. Moreover, it is preferable that it is 5 to 100 weight%, and, as for solid content concentration, it is more preferable that it is 20 to 50 weight%.

<Other ingredients>

The photosensitive resin composition which concerns on this invention can contain additives, such as surfactant, an adhesive improving agent, a thermal-polymerization inhibitor, and an antifoamer, as needed. As any additive, a conventionally well-known thing can be used. Examples of the surfactant include compounds such as anionic, cationic, and nonionic, conventionally known silane coupling agents as the adhesion improving agent, and hydroquinone and hydroquinone monoethyl ether as the thermal polymerization inhibitor. , as an antifoaming agent, a silicone-based compound, a fluorine-based compound, and the like can be given.

<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, or a sand mill, and filtration with a filter such as a 5 μm membrane filter if necessary.

≪Pattern Forming Method≫

In order to form a pattern using the photosensitive resin composition of the present invention, first, 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) or a curtain flow coater is used to form a photosensitive resin composition. A resin composition is applied on a substrate to form a coating film.

Then, the coating film is dried as needed. The drying method is not particularly limited, and for example, (1) a method of drying for 60 to 120 seconds at a temperature of 80 to 120 ° C., preferably 90 to 100 ° C. on a hot plate, (2) several hours to several hours at room temperature The method of leaving it to stand for a day, (3) the method of putting in a warm-air heater or an infrared heater for several tens of minutes - several hours, the method of removing a solvent, etc. are mentioned.

Next, the coating film on the substrate is positionally selectively exposed by irradiating active energy rays such as infrared rays or excimer laser light through a negative mask. Although the energy dose to irradiate also changes with the composition of the photosensitive resin composition, for example, ^{about 30-2000 mJ/cm<2>} is preferable.

A pattern of a desired shape is formed by developing the position-selectively exposed coating film with a developer. The developing method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. As a developing solution, organic things, such as monoethanolamine, diethanolamine, and triethanolamine, aqueous solutions, such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and a quaternary ammonium salt, are mentioned.

Next, it is preferable to post-baking at about 200 degreeC - 250 degreeC with respect to the pattern of a developing solution.

The pattern formed by the method described above using the photosensitive resin composition according to the present invention is suitably used for various purposes because it has excellent adhesion to a substrate and water resistance. In particular, in the black matrix provided in various display devices typified by liquid crystal display devices, it is strongly required to have excellent adhesion to a substrate and excellent water resistance from the viewpoint of product reliability. For this reason, in the photosensitive resin composition which concerns on this invention, the pattern formed using the photosensitive resin composition containing the coloring agent containing a light-shielding agent is used suitably 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 Examples, the following compounds 1 to 8 were used as the silane coupling agent. In the comparative example, the following compounds 9-17 were used as a silane coupling agent.

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

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-neck flask, and here It was dissolved by heating at 90-100° C. while blowing air at a rate of 25 ml/min. Then, while the solution was in a cloudy state, the temperature was gradually increased, and the solution was completely dissolved by heating at 120°C. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. In the meantime, the acid value was measured, and heating and stirring were continued until it became less than 1.0 mg KOH/g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature, and obtained the bisphenol fluorene type epoxy acrylate which is colorless and transparent and is represented by following formula (a-4) of a solid state.

Next, 600 g of 3-methoxybutyl acetate was added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate obtained in this way, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethyl ammonium bromide were mixed, and the temperature was gradually increased to 110 The reaction was carried out at -115°C for 4 hours. After confirming disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, followed by reaction at 90° C. for 6 hours to obtain Resin (A-1). The disappearance of the acid anhydride group was confirmed by the IR spectrum. In addition, this resin (A-1) corresponds to resin represented by said Formula (a-1).

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

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

In Examples and Comparative Examples, the 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 as a colorant.

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

100 parts by weight of alkali-soluble resin (resin (A-1)), 35 parts by weight of a photopolymerizable monomer (DPHA), 15 parts by weight of a photoinitiator, 3 parts by weight of a silane coupling agent of the kind shown in Table 1, and carbon black After mixing 500 parts by weight of the dispersion, the mixture was diluted with an organic solvent to a solid content concentration of 15% by weight to obtain a photosensitive resin composition. As the organic solvent used for dilution of the mixture, 3-methoxybutyl acetate (MA), propylene glycol monomethyl ether acetate (PM), and cyclohexanone (AN) were MA/PM/AN = 60/20/20 (weight ratio). ) was used as a mixed solvent. About the obtained photosensitive resin composition, the following method evaluated fine wire adhesiveness and water resistance.

(Evaluation of thin wire adhesion)

The photosensitive resin composition was applied on a glass substrate (100 mm×100 mm) using a spin coater, and prebaked at 90° C. for 120 seconds to form a coating film having a thickness of 1.0 μm. Next, using a Miller projection aligner (product name: TME-150RTO, manufactured by Topcon Co., Ltd.), the exposure gap was set to 50 µm, and the coating film was irradiated with ultraviolet rays through a negative mask having a pattern of 5 µm in width. The exposure dose was set to 4 steps of 10, 20, 40, and 100 mJ/cm ^{2 .} After the exposure coating film was developed for 50 seconds in a 0.04 wt% KOH aqueous solution at 26°C, post-baking was performed at 230°C for 30 minutes to form a line pattern.

The line pattern formed at each exposure dose was observed with the optical microscope, and thin wire|wire adhesiveness was evaluated. The case where peeling from the board|substrate was not observed in the formed pattern was judged as "good|favorableness". The case where a part or all of the formed pattern peeled from the board|substrate and the pattern of a desired shape could not be formed was judged as "defective". The determination of the fine wire adhesiveness of the photosensitive resin composition of each Example and a comparative example is described in Table 1 for each exposure amount.

(Water resistance evaluation)

It carried out similarly to evaluation of thin wire|wire adhesiveness, and formed the coating film with a film thickness of 1.0 micrometer on the glass substrate. The formed coating film was exposed without interposing a mask at an exposure amount of 100 mJ/cm ² to form a cured film on the glass substrate. Water resistance was evaluated using the formed cured film. The glass substrate provided with a cured film was left still in a pressure-resistant container for 24 hours in 120 degreeC, 2 atmospheres, and the atmosphere of 100% of 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 a glass substrate was observed. The case where peeling of the cured film from a glass substrate was not observed was judged as "good|favorableness". The case where peeling of the cured film from a glass substrate was observed was determined as "defect".

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 error error error error Comparative Example 2 compound 10 Good Good Good Good Comparative Example 3 compound 11 error error error error Comparative Example 4 compound 12 Good Good Good Good Comparative Example 5 compound 13 error error Good Good Comparative Example 6 compound 14 error error error Good Comparative Example 7 compound 15 error error Good Good Comparative Example 8 compound 16 error error error Good Comparative Example 9 compound 17 error error error 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 error error error Comparative Example 3 compound 11 error error error error Comparative Example 4 compound 12 Good error error error Comparative Example 5 compound 13 error error error error 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 error

[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 replaced with a dispersion of a perylene pigment having the following structure (solid content: 20 wt%, solvent: 3-methoxybutyl acetate). Thin wire adhesiveness and water resistance were evaluated similarly to Examples 2 and 4 using the obtained photosensitive resin composition. Table 3 shows the determination of the fine wire adhesion and the 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 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 Tables 1 to 3, including an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and a colorant, the photosensitive resin composition of an embodiment containing the compound represented by the above-mentioned formula (1) as a silane coupling agent Using the photosensitive resin composition If it is a formed pattern, it turns out that the adhesiveness with respect to the board|substrate of a favorable pattern and favorable water resistance are compatible.

On the other hand, from Tables 1 and 2, an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and a colorant, but does not contain the compound represented by the above formula (1) as a silane coupling agent Photosensitive resin composition of a comparative example It can be seen that the pattern formed by using is not compatible with the adhesion to the substrate of the good pattern and good water resistance.

In particular, according to Comparative Examples 6 to 8, with respect to the silane coupling agent contained in the photosensitive resin composition, when the heterocyclic ring directly connected to the -NH-CO-NH- group is a nitrogen-containing 5-membered ring, formed using the photosensitive resin composition It can be seen that even if the pattern has excellent water resistance, the fine wire adhesion is poor.

In addition, according to Comparative Example 9, when a benzene ring is directly connected 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, It can be seen that the water resistance is slightly lowered.

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

After mixing 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 photoinitiator and 3 parts by weight of a silane coupling agent of the kind shown in Table 2, the mixture was diluted with an organic solvent to a solid content concentration of 15% by weight to obtain a photosensitive resin composition. As an organic solvent used for dilution of the mixture, 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. About the obtained photosensitive resin composition, it carried out similarly to Example 1, and evaluated the fine wire adhesiveness 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 error error error error Comparative Example 11 compound 10 Good Good Good Good Comparative Example 12 compound 11 error error error Good Comparative Example 13 compound 12 error Good Good Good Comparative Example 14 compound 13 error error Good Good Comparative Example 15 compound 14 error error error Good Comparative Example 16 compound 15 error error Good Good Comparative Example 17 compound 16 error error error Good Comparative Example 18 compound 17 error error error 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 error error error Comparative Example 12 compound 11 Good error error error Comparative Example 13 compound 12 Good Good error error Comparative Example 14 compound 13 error error error error 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 Tables 5 and 6, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, and a pattern formed using the photosensitive resin composition of an embodiment comprising the compound represented by Formula (1) as a silane coupling agent. If it is, it turns out that the adhesiveness to the board|substrate of a favorable pattern and favorable water resistance can be compatible.

On the other hand, from Tables 5 and 6, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator are included, but the photosensitive resin composition of a comparative example that does not contain the compound represented by the above formula (1) as a silane coupling agent is used. It can be seen that the pattern formed by doing this is not compatible with the adhesion to the substrate of the good pattern and good water resistance.

In particular, according to Comparative Examples 15 to 18, with respect to the silane coupling agent included in the photosensitive resin composition, when the ring directly connected to the -NH-CO-NH- group is a nitrogen-containing 5-membered ring or a benzene ring, formed using the photosensitive resin composition It can be seen that even if the pattern has excellent water resistance, the fine wire adhesion is poor.

Claims (6)

(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photoinitiator, and (D) a silane coupling agent,
The photosensitive resin composition wherein the (D) 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 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-, R ⁴ is a single bond, X is a nitrogen-containing heteroaryl group which may have a substituent or may be monocyclic or polycyclic, ^{a ring bonded to -YR 4} - in X is a nitrogen-containing 6-membered aromatic ring, and -YR ⁴ - is a nitrogen-containing 6-membered aromatic ring in the ring. binds to carbon atoms). The method according to claim 1,
The photosensitive resin composition further containing (E) a coloring agent. 3. The method according to claim 2,
The photosensitive resin composition in which the said (E) colorant is a light-shielding agent. The process of apply|coating the photosensitive resin composition of any one of Claims 1-3 on a board|substrate to form a coating film;
a step of positionally selectively exposing the coating film;
A pattern forming method comprising the step of developing the exposed coating film. The black matrix formed using the photosensitive resin composition of Claim 3. A display device comprising the black matrix according to claim 5 .