JP6309755B2 - Photosensitive resin composition - Google Patents

Description

  This invention was formed using the photosensitive resin composition, the pattern formation method using the said photosensitive resin composition, and the photosensitive resin composition which contains a light-shielding agent as a coloring agent among the said photosensitive resin compositions. The present invention relates to a black matrix and a display device including the black matrix.

  A pattern formed using a 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 pattern formed using a photosensitive resin composition is used as a black matrix and RGB subpixels constituting a color filter, or a black column spacer.

  Examples of the photosensitive resin composition used in such applications include a photosensitive resin composition containing an alkali-soluble resin having a specific structure, a photopolymerization initiator, a photopolymerizable monomer, and a colorant. Known (Patent Document 1).

JP 2006-079064 A

  For patterns formed using photosensitive resin compositions used in electrical and electronic equipment typified by display devices, adhesion to substrates, high temperature and high humidity for the purpose of improving the reliability of equipment operation. There is a demand for improved water resistance that can withstand use under conditions. Although the pattern formed using the photosensitive resin composition described in Patent Document 1 is excellent to some extent in terms of adhesion to a substrate and water resistance, further improvement is required for these characteristics.

  The present invention has been made in view of the above problems, and a photosensitive resin composition capable of forming a pattern excellent in adhesion to a substrate and water resistance, and a pattern forming method using the photosensitive resin composition, An object of the present invention is to provide a black matrix formed using a photosensitive resin containing a light-shielding agent as a colorant in the photosensitive resin composition, and a display device including the black matrix.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, (D) a silane coupling agent having a specific structure is blended with a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator. Thus, the inventors have found that the above-described problems can be solved, and have completed the present invention. Specifically, the present invention provides the following.

The first aspect of the present invention includes (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent.
(D) The photosensitive resin composition whose silane coupling agent is a compound represented by following formula (1).
_{^{R 1 m R 2 (3-}} m) Si-R 3 -NH-C (O) -Y-R 4 -X ··· (1)
(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, and Y is —NH— or —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 and may be monocyclic or polycyclic, The ring bonded to —Y—R ⁴ — is a nitrogen-containing 6-membered aromatic ring, and —Y—R ⁴ — is bonded to the carbon atom in the nitrogen-containing 6-membered aromatic ring.

A second aspect of the present invention includes a step of applying a photosensitive resin composition according to the first aspect on a substrate to form a coating film;
A step of selectively exposing the coating film;
And a step of developing the exposed coating film.

  3rd aspect of this invention is a black matrix formed using the photosensitive resin composition which contains a 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 excellent in adhesion to a substrate and water resistance, a pattern forming method using the photosensitive resin composition, and coloring among the photosensitive resin compositions A black matrix formed using a photosensitive resin composition containing a light-shielding agent as an agent, and a display device including the black matrix can be provided.

≪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. Including. Hereinafter, essential or optional components contained in the photosensitive resin composition according to the present invention will be described in order.

<(A) Alkali-soluble resin>
(A) An alkali-soluble resin (hereinafter also referred to as “component (A)”) is a resin solution having a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate). When the film is immersed in a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute, the film thickness is 0.01 μm or more.

  (A) The alkali-soluble resin is not particularly limited as long as it is a resin exhibiting alkali solubility as described above, and can be appropriately selected from conventionally known resins. (A) As resin suitable as alkali-soluble resin, (A1) resin which has a cardo structure is mentioned.

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

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

In the above formula (a-2), each R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, each R ^a2 independently represents a hydrogen atom or a methyl group, 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 obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

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

  (A1) The mass average molecular weight of the resin having a cardo structure is preferably 1000 to 40000, and more preferably 2000 to 30000. By setting it as the above range, sufficient heat resistance and film strength can be obtained while obtaining good 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 such resins, since it is easy to obtain a photosensitive resin composition that gives a pattern having excellent breaking strength and adhesion to a substrate, (a1) an unsaturated carboxylic acid and (a2) an epoxy group-containing unsaturated compound (A2) copolymer obtained by polymerizing at least.

  (A1) Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Etc. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These (a1) unsaturated carboxylic acids can be used alone or in combination of two or more.

  Examples of the (a2) epoxy group-containing unsaturated compound include (a2-I) an unsaturated compound having an alicyclic epoxy group and (a2-II) an unsaturated compound having no alicyclic epoxy group, (A2-I) An unsaturated compound having an alicyclic epoxy group is 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. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a2-I) alicyclic epoxy group-containing unsaturated compounds can 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 these, in order to moderate developability, compounds represented by the following formulas (a2-1) to (a2-6) are preferable, and the following formulas (a2-1) to (a2-4) are preferable. The compounds represented are more preferred.

In the above 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, and R ¹³ represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ¹² is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. Examples of R ¹³ include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

  (A2-II) As an epoxy group-containing unsaturated compound having no alicyclic group, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, (Meth) acrylic acid epoxy alkyl esters such as 7-epoxyheptyl (meth) acrylate; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylic acid Α-alkyl acrylic acid epoxy alkyl esters such as 6,7-epoxyheptyl; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable from the viewpoint of copolymerization reactivity and the strength of the cured resin. These (a2-II) epoxy group-containing unsaturated compounds having no alicyclic group can be used alone or in combination of two or more.

  (A2) The copolymer polymerized (a3) an alicyclic group-containing unsaturated compound having no epoxy group, together with the above (a1) unsaturated carboxylic acid and (a2) an epoxy group-containing unsaturated compound. It may be a thing.

  The (a3) alicyclic group-containing unsaturated compound is not particularly limited as long as it is an unsaturated compound having an alicyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. These (a3) alicyclic group-containing unsaturated compounds can be used alone or in combination of two or more.

  Specifically, examples of the (a3) alicyclic group-containing unsaturated compound include compounds represented by the following formulas (a3-1) to (a3-7). In these, since it is easy to obtain the photosensitive resin composition with favorable developability, the compounds represented by the following formulas (a3-3) to (a3-8) are preferable, and the following formula (a3-3), The compound represented by (a3-4) is more preferable.

In the above formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ²² is preferably a single bond or a linear or branched alkylene group such as 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, for example, a methyl group or an ethyl group.

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

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (Meth) acrylamides include (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 and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether. Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

  Styrenes 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, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  The proportion of the structural unit derived from the (a1) unsaturated carboxylic acid in the (A2) copolymer is preferably 1 to 25% by mass, and more preferably 8 to 16% by mass. Moreover, it is preferable that the ratio of the structural unit derived from the said (a3) alicyclic group containing unsaturated compound in the (A2) copolymer is 1-30 mass%, and it is 5-20 mass%. More preferred.

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

  (A2) The weight average molecular weight of the copolymer (Mw: measured value in terms of polystyrene of gel permeation chromatography (GPC). Same in this specification) is preferably 2000 to 200000, and preferably 5000 to 30000. It is more preferable. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

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

  Further, (A) the alkali-soluble resin has at least a structural unit derived from the above (a1) unsaturated carboxylic acid and a structural unit having a polymerizable site with (B) a photopolymerizable monomer described later (A3). Polymerization of a copolymer or a structural unit derived from the above (a1) unsaturated carboxylic acid, a structural unit derived from the above (a2) epoxy group-containing unsaturated compound, and a photopolymerizable monomer (B) described later A resin containing (A4) a copolymer having at least a structural unit having a possible site can also be suitably used. (A) When alkali-soluble resin contains (A3) copolymer or (A4) copolymer, the adhesiveness to the board | substrate of the photosensitive resin composition and the fracture strength after hardening of the photosensitive resin composition are improved. be able to.

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

  (B) The structural unit which has a site | part polymerizable with a photopolymerizable monomer has an ethylenically unsaturated group as a site | part polymerizable with (B) photopolymerizable monomer. The (A3) copolymer is prepared by reacting at least a part of the carboxyl group contained in the homopolymer of the (a1) unsaturated carboxylic acid and the (a2) epoxy group-containing unsaturated compound. can do. The (A4) copolymer is an epoxy group in a copolymer having the structural unit derived from the (a1) unsaturated carboxylic acid and the structural unit derived from the (a2) epoxy group-containing unsaturated compound. It can be prepared by reacting at least a portion with (a1) an unsaturated carboxylic acid.

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

  (A) The content of the alkali-soluble resin is preferably 30 to 90% by mass and more preferably 45 to 75% by mass with respect to the solid content of the photosensitive resin composition. By setting it as the above range, there is a tendency that developability is easily balanced.

  (B) The structural unit which has a site | part polymerizable with a photopolymerizable monomer has an ethylenically unsaturated group as a site | part polymerizable with (B) photopolymerizable monomer. The copolymer (A2) is a part of the epoxy group in the copolymer having the structural unit derived from the (a1) unsaturated carboxylic acid and the structural unit derived from the (a2) epoxy group-containing unsaturated compound. And (a1) an unsaturated carboxylic acid.

  The mass average molecular weight of the copolymer (A2) is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the above range, the film forming ability of the photosensitive resin composition and the developability after exposure tend to be easily balanced.

  (A) The content of the alkali-soluble resin is preferably 30 to 90% by mass and more preferably 45 to 75% by mass with respect to the solid content of the photosensitive resin composition. By setting it as the above range, there is a tendency that developability is easily balanced.

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

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 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 ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

  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 (meta Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) 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, diglycidyl phthalate ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (Meth) acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-bidoxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene Examples thereof include polyfunctional monomers such as ethers, polyhydric alcohols and N-methylol (meth) acrylamide condensates, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

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

  The content of the component (B) is preferably 5 to 60% by mass and more preferably 10 to 50% by mass with respect to the solid content of the photosensitive resin composition. By setting it as the above range, it tends to be easy to balance sensitivity, developability, and resolution.

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

  Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 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-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [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-carbazol-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, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 -Butyl dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoa Benzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimida , 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 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-dimethylaminopropio Enone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, 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 (tri Loromethyl) -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 (trichloromethyl) -s -Triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) ) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-) 4-methoxy) styrylphenyl-s-triazine and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  Among these, it is particularly preferable in terms of sensitivity to use an oxime-based photopolymerization initiator. Among oxime-based photopolymerization initiators, particularly preferred are ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyl). Oxime), 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 content of a component is 0.5-30 mass% with respect to solid content of the photosensitive resin composition, and it is more preferable that it is 1-20 mass%. By making content of (C) component into said range, the photosensitive resin composition which can form the pattern which is excellent in water resistance can be obtained.

  Moreover, you may combine a photoinitiator adjuvant with this (C) component. Examples of the photoinitiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoic acid 2- Ethylhexyl, 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-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, pentaerythritol tetra-mercapto acetate, thiol compounds such as 3-mercapto propionate. These photoinitiation assistants can be used alone or in combination of two or more.

<(D) Silane coupling agent>
The photosensitive resin composition according to the present invention contains a silane coupling agent represented by the following formula (1). For this reason, the pattern with favorable adhesiveness to a board | substrate and water resistance can be formed by using the photosensitive resin composition which concerns on this invention. The photosensitive resin composition may contain a combination of two or more silane coupling agents represented by the formula (1).

_{^{R 1 m R 2 (3-}} m) Si-R 3 -NH-C (O) -Y-R 4 -X ··· (1)
(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, and Y is —NH— or —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 and may be monocyclic or polycyclic, The ring bonded to —Y—R ⁴ — is a nitrogen-containing 6-membered aromatic ring, and —Y—R ⁴ — is bonded to the carbon atom in the nitrogen-containing 6-membered aromatic ring.

In formula (1), R ¹ is an alkoxy group. For R ^1, number of carbon atoms in the alkoxy group 1 to 6, more preferably 1 to 4, (D) from the viewpoint of the reactivity of the silane coupling agent 1 or 2 are particularly preferred. Preferable 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.

The silanol group produced by hydrolysis of R ¹ that is an alkoxy group reacts with the surface of the substrate and the like, thereby improving the adhesion of the pattern formed using the photosensitive resin composition to the substrate surface. For this reason, m is preferably 3 from the viewpoint of improving the adhesion of the pattern to the substrate surface.

In formula (1), R ² is an alkyl group. For R ^2, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, (D) from the viewpoint of the reactivity of the silane coupling agent 1 or 2 are particularly preferred. Preferred 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, and n-hexyl group. N-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.

In formula (1), R ³ is an alkylene group. For R ^3, carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 6, 2 to 4 are particularly preferred. Preferable specific examples of R ³ include a 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, hexane-1,6-diyl group, heptane-1,7- And 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. It is done. Among these alkylene groups, 1,2-ethylene group, propane-1,3-diyl group, and butane-1,4-diyl group are preferable.

  Y is —NH—, —O—, or —S—, and is preferably —NH—. Since the bond represented by —CO—NH— is less susceptible to hydrolysis than the bond represented by —CO—O— or —CO—S—, a compound in which Y is —NH— is represented by (D ) When a photosensitive resin composition contained as a silane coupling agent is used, a pattern having excellent water resistance can be easily formed.

R ⁴ is a single bond or an alkylene group, and preferably a single bond. Preferable examples when R ⁴ is an alkylene group are the same as those for R ³ .

X is a nitrogen-containing heteroaryl group which may have a substituent and may be monocyclic or polycyclic, and the ring bonded to —Y—R 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. Although the reason is unknown, when a photosensitive resin composition containing such a compound having X as the (D) silane coupling agent is used, a pattern having excellent adhesion to the 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 monocycles are condensed or a group in which a plurality of monocycles are bonded via 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 6-membered aromatic ring in X may or may not contain a hetero atom, and may be an aromatic ring or an aromatic ring. It does not have to be a ring.

  Examples of the substituent that X which is a 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, C2-C6 alkenyloxy group, C2-C6 aliphatic acyl group, benzoyl group, nitro group, nitroso group, amino group, hydroxy group, mercapto group, cyano group, sulfonic acid group, carboxyl group And halogen atoms. The number of substituents X has is not particularly limited as long as the object of the present invention is not impaired. The number of substituents X has 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 formula.

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

Preferable 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 mass and more preferably 0.5 to 7% by mass with respect to the solid content of the photosensitive resin composition excluding the colorant. . By making content of (D) 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 according to the present invention may further contain (E) a colorant.

  The (E) colorant contained in the photosensitive resin composition according to the present invention is not particularly limited. For example, in the color index (CI; issued by The Society of Dyers and Colorists), pigment (Pigment) It is preferable to use a compound classified under (), specifically, a compound with a color index (CI) number as shown below.

  Examples of yellow pigments that can be suitably used include C.I. I. Pigment Yellow 1 (hereinafter, “CI Pigment Yellow” is the same, and only the number is 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.

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

  Examples of red pigments that can be suitably used include C.I. I. Pigment Red 1 (hereinafter, “CI Pigment Red” is the same, and only the number is 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: 1, 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, 1 8, 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. I. Pigment Blue 1 (hereinafter, “CI Pigment Blue” is the same, and only the number is described) 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 , And 66.

  Examples of pigments of other hues that can be suitably used include C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment Green 37 and other green pigments, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigments such as CI Pigment Brown 28, C.I. I. Pigment black 1, C.I. I. And black pigments such as CI Pigment Black 7.

  When the colorant is a light shielding agent, it is preferable to use a black pigment or a purple pigment as the 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, composite oxides, metal sulfides In addition, various pigments can be mentioned regardless of organic matter or inorganic matter such as metal sulfate or metal carbonate. Among these, it is preferable to use carbon black having high light shielding properties.

  As the carbon black, known carbon blacks 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.

  A perylene pigment is also preferable as the light-shielding agent. Specific examples of the perylene pigment include the perylene pigment represented by the following formula (e-1), the perylene pigment represented by the following formula (e-2), and the following formula (e-3). Perylene pigments. As commercial products, product names K0084 and K0086 manufactured by BASF, Pigment Black 21, 30, 31, 32, 33, 34, and the like can be preferably used as perylene pigments.

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

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

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

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

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

In formula (e-3), R ^e7 and R ^e8 are each independently a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, and may contain a heteroatom of N, O, S, or P. Good. When R ^e7 and R ^e8 are alkyl groups, the alkyl group 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) include, for example, JP-A-62-17353. Can be synthesized using the method described in JP-B 63-26784. That is, perylene-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine are used as raw materials, and a heating reaction is performed in water or an organic solvent. The target product can be obtained by reprecipitation of the obtained crude product in sulfuric acid or recrystallization in water, an organic solvent or a mixed solvent thereof.

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

  The light-shielding agent may contain a dye having a hue such as red, blue, green, and yellow together with the black pigment and the purple pigment for the purpose of adjusting the color tone. The pigment of other hues of the black pigment and the purple pigment can be appropriately selected from known pigments. For example, the above-mentioned various pigments can be used as the coloring matter of other hues of black pigments and purple pigments. The amount of the dye having a hue other than the black pigment or the purple pigment is preferably 15% by mass or less and more preferably 10% by mass or less with respect to the total mass 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 dispersant, it is preferable to use a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant. 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, but when used in combination, the organic pigment is used in an amount of 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the inorganic pigment and the organic pigment Preferably, it is used in the range of 20 to 40 parts by mass.

  The amount of the colorant used in the photosensitive resin composition can be appropriately selected within a range that does not impair the object of the present invention, and is typically 5 to 5 parts by mass relative to the total solid content of the photosensitive resin composition. 70 mass parts is preferable and 25-60 mass parts is more preferable.

  The colorant is preferably added to the photosensitive resin composition after making it into a dispersion dispersed at an appropriate concentration using a dispersant.

<(S) Organic solvent>
The photosensitive resin composition according to the present invention preferably contains (S) an organic solvent (hereinafter, also referred to as “component (S)”) for improving coating properties and adjusting 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-n-propyl ether, propylene glycol mono-n-butyl ether , Dipropylene glycol monomethyl ether, (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; ethylene (Poly) alkylene glycol monoalkyl ether acetates such as 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 Diethylene Other ethers such as recall dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Alkyl 2-lactic acid esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 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-butyrate Other esters such as -propyl, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate; toluene, xylene Aromatic hydrocarbons such as N-methylpyrrolidone, N, N-dimethylformamide, amides such as N, N-dimethylacetamide, and the like. Among these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, other ethers described above, alkyl lactate esters, and other esters described above are preferable, alkylene glycol monoalkyl ether acetates described above. Other ethers and other esters described above are more preferred. These solvents can be used alone or in combination of two or more.

  The content of the component (S) is not particularly limited, and is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. The viscosity of the photosensitive resin composition is preferably 5 to 500 cp, more preferably 10 to 50 cp, and still more preferably 20 to 30 cp. Moreover, it is preferable that solid content concentration is 5-100 mass%, and it is more preferable that it is 20-50 mass%.

<Other ingredients>
The photosensitive resin composition according to the present invention may contain additives such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, and an antifoaming agent as necessary. Any additive can be used as the additive. Examples of the surfactant include anionic, cationic, and nonionic compounds, examples of the adhesion improver include conventionally known silane coupling agents, and examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone mono Examples of the antifoaming agent include silicone-based and fluorine-based compounds.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition according to the present invention is prepared by mixing (dispersing and kneading) each of the above components with a stirrer such as a three-roll mill, a ball mill, or a sand mill and, if necessary, filtering with a filter such as a 5 μm membrane filter. can do.

≪Pattern formation 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, a bar coater, a spinner (rotary coating device), a non-contact such as a curtain flow coater, etc. A photosensitive resin composition is applied onto a substrate using a mold coating apparatus to form a coating film.

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

Next, active energy rays such as ultraviolet rays and excimer laser light are irradiated through a negative mask to selectively expose the coating film on the substrate. 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 having a desired shape is formed by developing the coating film exposed to position selectively with a developer. The development method is not particularly limited, and for example, an immersion method, a spray 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.

  Next, it is preferable to perform post-baking on the developed pattern at about 200 ° C. to 250 ° C.

  Since the pattern formed by the method described above using the photosensitive resin composition according to the present invention is excellent in adhesion to the substrate and water resistance, it is suitably used in various applications. In particular, black matrices provided in various display devices typified by liquid crystal display devices are strongly required to have excellent adhesion to substrates and water resistance from the viewpoint of product reliability. For this reason, the pattern formed using the photosensitive resin composition containing the coloring agent containing a light-shielding agent among the photosensitive resin compositions which concern on this invention is used suitably as a black matrix.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

〔Example〕
In Examples, the following compounds 1 to 8 were used as silane coupling agents. In 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 was used as the alkali-soluble resin.
First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / 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 represented by the following transparent formula (a-4) colorless and transparent.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added. The mixture was gradually heated and reacted at 110 to 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 and reacted at 90 ° C. for 6 hours to obtain Resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum. In addition, this resin (A-1) is corresponded to resin represented by the said Formula (a-1).

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

  In 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, as a colorant, a carbon black dispersion (CF black (manufactured by Gokoku Color Co., Ltd.)) in which carbon black is dispersed in 3-methoxybutyl acetate, a solid content concentration of 25% by mass. ) Was used.

[Examples 1-8 and Comparative Examples 1-9]
100 parts by mass of an alkali-soluble resin (resin (A-1)), 35 parts by mass of a photopolymerizable monomer (DPHA), 15 parts by mass of a photopolymerization initiator, and a silane coupling agent of the type shown in Table 1 and 3 After mixing parts by mass with 500 parts by mass of carbon black dispersion, the mixture was diluted with an organic solvent to a solid content concentration of 15% by mass to obtain a photosensitive resin composition. Organic solvent used for dilution of the mixture As a mixture, 3-methoxybutyl acetate (MA), propylene glycol monomethyl ether acetate (PM), and cyclohexanone (AN) are mixed at MA / PM / AN = 60/20/20 (mass ratio). Solvent was used. About the obtained photosensitive resin composition, according to the following method, fine wire adhesiveness and water resistance were evaluated.

(Thin wire adhesion evaluation)
The photosensitive resin composition was applied onto a glass substrate (100 mm × 100 mm) using a spin coater and pre-baked at 90 ° C. for 120 seconds to form a coating film having a thickness of 1.0 μm. Next, using a mirror projection aligner (product name: TME-150 RTO, manufactured by Topcon Corporation), the exposure gap was 50 μm, and the coating film was irradiated with ultraviolet rays through a negative mask on which a pattern with a width of 5 μm was formed. The exposure amount was set to four levels of 10, 20, 40, and 100 mJ / cm ² . The exposed coating film was developed with a 0.04 mass% KOH aqueous solution at 26 ° C. for 50 seconds, and then post-baked at 230 ° C. for 30 minutes to form a line pattern.
The line pattern formed at each exposure amount was observed with an optical microscope to evaluate the fine line adhesion. The case where peeling from the substrate was not observed in the formed pattern was determined as “good”. A case where a part or all of the formed pattern was peeled off from the substrate and a pattern having a desired shape could not be formed was determined as “bad”. The determination of the fine wire adhesion of the photosensitive resin compositions of each Example and Comparative Example is shown in Table 1 for each exposure amount.

(Water resistance evaluation)
A coating film having a thickness of 1.0 μm was formed on a glass substrate in the same manner as in the evaluation of fine wire adhesion. The formed coating film is exposed at an exposure amount of 100 mJ / cm ² without using a mask, and a cured film is formed on the glass substrate. Water resistance was evaluated using the formed cured film. The glass substrate provided with the cured film was allowed to stand in a pressure-resistant container for 24 hours in an atmosphere of 120 ° C., 2 atmospheres and 100% humidity. At 2 hours, 6 hours, 12 hours, and 24 hours, the glass substrate was taken out of the pressure vessel, and the presence or absence of peeling of the cured film from the glass substrate was observed. The case where peeling of the cured film from the glass substrate was not observed was judged as “good”. The case where peeling of the cured film from the glass substrate was observed was judged as “bad”.

[Examples 9 and 10]
Photosensitivity in the same manner as in Examples 2 and 4, except that the carbon black dispersion was changed to a perylene pigment dispersion having the following structure (solid content: 20% by mass, solvent: 3-methoxybutyl acetate). A resin composition was obtained. Using the obtained photosensitive resin composition, fine wire adhesion and water resistance were evaluated in the same manner as in Examples 2 and 4. Table 3 shows the determination of fine wire adhesion and the determination of water resistance.

  From Tables 1-3, examples of the examples containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a colorant, and a compound represented by the above formula (1) as a silane coupling agent. If it is a pattern formed using the photosensitive resin composition, it turns out that the adhesiveness to the board | substrate of a favorable pattern and favorable water resistance can be made compatible.

  On the other hand, from Table 1 and Table 2, it contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a colorant, and the compound represented by the above formula (1) is used as a silane coupling agent. It turns out that the pattern formed using the photosensitive resin composition of the comparative example which does not contain cannot adhere | attach both the adhesiveness to the board | substrate of a favorable pattern, and favorable 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, Even if the pattern formed using a resin composition is excellent in water resistance, it turns out that it is inferior to fine wire adhesiveness.

  Further, according to Comparative Example 9, the silane coupling agent contained in the photosensitive resin composition is formed using the photosensitive resin composition when the benzene ring is directly bonded to the —NH—CO—NH— group. It can be seen that the pattern to be formed is inferior in fine wire adhesion and slightly inferior in water resistance.

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

  58.5 parts by mass of an alkali-soluble resin (resin (A-2)), 40 parts by mass of a photopolymerizable monomer (DPHA), 1.5 parts by mass of a photopolymerization initiator, and a silane cup of the type shown in Table 2 After mixing the ring agent and 3 parts by mass, the mixture was diluted with an organic solvent to a solid content concentration of 15% by mass to obtain a photosensitive resin composition. The organic solvent used for diluting the mixture was diethylene glycol methyl. A mixed solvent in which ethyl ether (MEDG) and propylene glycol monomethyl ether acetate (PM) were mixed at MEDG / PM = 60/40 / (mass ratio) was used. About the obtained photosensitive resin composition, it carried out similarly to Example 1, and evaluated fine wire adhesiveness and water resistance.

  From Table 5 and Table 6, the photosensitive resin of the Example which contains alkali-soluble resin, a photopolymerizable monomer, and a photoinitiator, and contains the compound represented by the above-mentioned formula (1) as a silane coupling agent. It can be seen that a pattern formed using the composition can achieve both good adhesion to a substrate having a good pattern and good water resistance.

  On the other hand, from Tables 5 and 6, a comparative example containing an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, but not containing the compound represented by the above formula (1) as a silane coupling agent. It can be seen that the pattern formed using this photosensitive resin composition cannot achieve both good adhesion of the pattern to the substrate and good water resistance.

  In particular, according to Comparative Examples 15 to 18, for the silane coupling agent contained 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, It can be seen that the pattern formed using the photosensitive resin composition is inferior in fine wire adhesion even though it is excellent in water resistance.

Claims (9)

A photosensitive resin composition used in a pattern forming method comprising an exposure step and a development step,
(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a silane coupling agent, and (E) a colorant,
The photosensitive resin composition whose said (D) silane coupling agent is a compound represented by following formula (1).
_{^{R 1 m R 2 (3-}} m) Si-R 3 -NH-C (O) -Y-R 4 -X ··· (1)
(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 and may be monocyclic or polycyclic, and the ring bonded to —Y—R ⁴ — in X is nitrogen-containing (It is a 6-membered aromatic ring, and —YR ⁴ — is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring.)   The photosensitive resin composition of Claim 1 whose said (E) coloring agent is a light-shielding agent. A photosensitive resin composition used in a pattern forming method comprising an exposure step and a development step,
(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent,
The (D) silane coupling agent is a compound represented by the following formula (1):
The (A) alkali-soluble resin is a photosensitive resin composition containing (A1) a resin having a cardo structure.
_{^{R 1 m R 2 (3-}} m) Si-R 3 -NH-C (O) -Y-R 4 -X ··· (1)
(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 and may be monocyclic or polycyclic, and the ring bonded to —Y—R ⁴ — in X is nitrogen-containing (It is a 6-membered aromatic ring, and —YR ⁴ — is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring.) A photosensitive resin composition used in a pattern forming method comprising an exposure step and a development step,
(A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a silane coupling agent,
The (D) silane coupling agent is a compound represented by the following formula (1):
The (A) alkali-soluble resin is a photosensitive resin composition containing a resin having an alicyclic group in its structure ,
The resin having the alicyclic group is represented by the following formulas (a2-1), (a2-2), (a2-3), (a2-4), (a2-5), (a2-6), (a2 -7), (a2-8), (a2-9), (a2-10), (a2-11), (a2-12), (a2-13), (a2-14), (a2-15) ) And (a2-16), a photosensitive resin composition that is a polymer of one or more compounds represented by at least one formula .
_{^{R 1 m R 2 (3-}} m) Si-R 3 -NH-C (O) -Y-R 4 -X ··· (1)
(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 and may be monocyclic or polycyclic, and the ring bonded to —Y—R ⁴ — in X is nitrogen-containing (It is a 6-membered aromatic ring, and —YR ⁴ — is bonded to a carbon atom in the nitrogen-containing 6-membered aromatic ring.)

(In formulas (a2-1) to (a2-16), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a C 1-6 divalent aliphatic saturated hydrocarbon group, and R ¹³ represents A C1-C10 bivalent hydrocarbon group is shown, n shows the integer of 0-10.)   Furthermore, the photosensitive resin composition of Claim 3 or 4 containing a coloring agent (E).   The photosensitive resin composition of Claim 5 whose said (E) coloring agent is a light-shielding agent. Applying the photosensitive resin composition according to any one of claims 1 to 6 on a substrate to form a coating film;
Exposing the coating film in a position-selective manner;
And developing the exposed coating film.   The black matrix comprised by the hardened | cured material of the photosensitive resin composition of Claim 2 or 6.   A display device comprising the black matrix according to claim 8.