TWI649622B - Photosensitive resin composition - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition which can form a pattern excellent in adhesion to a substrate and water resistance, a pattern forming method using the photosensitive resin composition, and a photosensitive resin composition. A black matrix formed of a photosensitive resin composition containing a sunscreen as a colorant, and a display device including the black matrix.

The solution of the present invention is to blend a specific structure of (D) decane in a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator. Coupling agent.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition, a pattern forming method using the photosensitive resin composition, and a black matrix formed using a photosensitive resin composition containing a light-shielding agent as a coloring agent in the photosensitive resin composition. And a display device having the black matrix.

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

As a photosensitive resin composition used for such a use, for example, an alkali-soluble resin having a specific structure, a photopolymerization initiator, a photopolymerizable monomer, and a photosensitive resin composition with a coloring agent are known (Patent Document 1).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-2006-079064

Electrical and electronic equipment represented by display devices In the pattern formed by the photosensitive resin composition to be used, the adhesion of the substrate is required for the purpose of improving the reliability of the operation of the machine, and the water resistance of the use under high temperature and high humidity conditions is also required. improve. In the pattern formed by the photosensitive resin composition described in Patent Document 1, although the adhesion to the substrate or the water resistance is excellent to some extent, further improvement of these characteristics is required.

The present invention has been completed in view of the above problems, and the object is 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 a coloring composition using the photosensitive resin composition A black matrix formed of a photosensitive resin of a light-shielding agent of the agent, and a display device including the black matrix.

The present inventors have repeated research focused on solving the above problems. As a result, it was found that a specific structure of (D) decane coupling agent was blended in a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator. The above problem can be solved and the present invention is finally completed. Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive resin composition comprising (A) an alkali-soluble resin, and (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a decane couple The mixture (D) decane 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. . . (1) (In the formula (1), R ¹ is an alkoxy group, R ² is an alkyl group, m is an integer of 1 to 3, R ³ is an alkyl group, and Y is -NH-, -O- or -S - R ⁴ is a single bond or an alkylene group, X may have a substituent or a monocyclic or polycyclic nitrogen-containing heteroaryl group, and a -YR ⁴ -bonded ring nitrogen-containing 6 member in X An aromatic ring, a -YR ⁴ - is bonded to a carbon atom in the aforementioned nitrogen-containing 6-membered aromatic ring).

A second aspect of the present invention is a method for forming a pattern, comprising: a step of applying a photosensitive resin composition of a first aspect onto a substrate to form a coating film, and selectively exposing the coating film to a position The step of developing a film with the exposed coating film.

The third aspect of the present invention is a black matrix formed by using a photosensitive resin composition containing a light-shielding agent as a colorant in the photosensitive resin composition of the first aspect.

A fourth aspect of the invention is a display device having a black matrix of a third aspect.

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a pattern excellent in adhesion to a substrate and water resistance, and to use the photosensitive material. A pattern forming method of the resin composition, a black matrix formed of a photosensitive resin composition containing a light-shielding agent as a coloring agent in the photosensitive resin composition, and a display device including the black matrix.

[Formation of the Invention] "Photosensitive Resin Composition"

The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and a (D) decane coupling agent having a specific structure. Hereinafter, the photosensitive resin composition of the present invention is contained, and necessary or optional components are described in order.

<(A) alkali soluble resin>

The (A) alkali-soluble resin (hereinafter also referred to as "(A) component)" means a resin solution (solvent: propylene glycol monomethyl ether acetate) having a resin concentration of 20% by mass, formed on a substrate. When the resin film having a thickness of 1 μm was immersed in a KOH aqueous solution having a concentration of 0.05% by mass for 1 minute, the film thickness was 0.01 μm or more.

(A) the alkali-soluble resin as long as it exhibits the above-described alkali solubility The resin is not particularly limited and can be suitably selected from conventional resins. As a suitable resin of (A) alkali-soluble resin, (A1) resin which has a cardo structure is mentioned.

As (A1) resin with a cardo structure, there is no special Other restrictions can be used with conventional resins. Among them, it is preferred to The resin shown in (a-1).

In the above formula (a-1), Xa represents the following formula (a-2) The base shown.

In the above formula (a-2), R ^a1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, and R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a represents a single bond or a formula The base shown in (a-3).

Further, in the above 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 the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl endomethylene tetrahydrophthalate. Anhydride, chloro-bromic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

Further, in the above formula (a-1), Z ^a represents ^a residue obtained by removing two acid anhydride groups from the tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

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

(A1) Mass average molecular weight of resin with cardo structure The amount is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By having the above range, sufficient heat resistance and film strength can be obtained while obtaining good developability.

As (A) alkali-soluble resin, (a1) can also be used. A copolymer of a saturated carboxylic acid and a copolymerized component other than the unsaturated carboxylic acid. Among such resins, from the viewpoint of easily obtaining a photosensitive resin composition having a pattern which is excellent in breaking strength or adhesion to a substrate, at least (a1) unsaturated carboxylic acid and (a2) are polymerized. (A2) copolymer of an epoxy group-containing unsaturated compound.

As the (a1) unsaturated carboxylic acid, (meth) propyl a monocarboxylic acid such as an acid or a crotonic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citric acid, mesaconic acid or itaconic acid; or an anhydride of such a dicarboxylic acid. Among these, (meth)acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, ease of availability, and the like. this The (a1) unsaturated carboxylic acid type may be used alone or in combination of two or more.

As (a2) an epoxy group-containing unsaturated compound, (a2-I) an unsaturated compound having an alicyclic epoxy group and (a2-II) an unsaturated compound having no alicyclic epoxy group, preferably (a2-I) having an alicyclic ring An unsaturated compound of an oxy group.

(a2-I) an unsaturated compound having an alicyclic epoxy group The alicyclic group constituting the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclic fluorenyl group, a tricyclic fluorenyl group, and a tetracyclic decyl group. The (a2-I) unsaturated compound containing an alicyclic epoxy group may be used alone or in combination of two or more.

Specifically, as (a2-I) containing an alicyclic epoxy group, Examples of the saturated compound include compounds represented by the following formulas (a2-1) to (a2-16). Among these, in order to make the developing property moderate, it is preferable to use a compound represented by the following formulas (a2-1) to (a2-6), and more preferably, the following formula (a2-1) to (a2) -4) The compound shown.

In the above formula, R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ¹³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10. R ^{12 is} preferably a linear or branched alkylene group such as methylene, ethyl, propyl, tetramethylene, ethyl ethyl, pentamethylene or hexamethylene. base. As R ¹³ , for example, a methylene group, an ethyl group, a propyl group, a tetramethylene group, an ethyl group ethyl group, a pentamethylene group, a hexamethylene group, a phenylene group, a cyclohexyl group, and a -CH are preferably used. ₂ -Ph-CH ₂ - (Ph represents a phenylene group).

An epoxy group having no alicyclic group as (a2-II) Examples of the unsaturated compound include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and (methyl). Ethoxyalkyl (meth)acrylates such as 6,7-epoxyheptyl acrylate; α-ethyl methacrylate, α-n-propyl propylene acrylate, α-n-butyl An α-alkyl acrylate epoxy alkoxylate such as glycidyl acrylate or α-ethyl acrylate 6,7-epoxyheptyl ester. Among these, from the viewpoints of copolymerization reactivity, resin strength after curing, and the like, preferably, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 6,7-epoxyheptyl (meth)acrylate. (a2-II) The epoxy group-containing unsaturated compound which does not have an alicyclic group may be used alone or in combination of two or more.

The (A2) copolymer may also be such that the above (a1) is unsaturated. The carboxylic acid and (a2) an epoxy group-containing unsaturated compound together with (a3) an alicyclic group-containing unsaturated compound having no epoxy group are polymerized.

As (a3) an unsaturated compound containing an alicyclic group, There is no particular limitation as long as it is an unsaturated compound having an alicyclic group. The alicyclic system can be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Further, examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclodecyl group, a tricyclodecanyl group, and a tetracyclododecyl group. These (a3) unsaturated compounds containing an alicyclic group may be used individually or in combination of 2 or more types.

Specifically, as (a3) an unsaturated group containing an alicyclic group The compound is, for example, a compound represented by the following formula (a3-1) to (a3-7). Among these, it is easy to obtain a photosensitive tree with good imaging properties. In view of the lipid composition, a compound represented by the following formulas (a3-3) to (a3-8) is preferred, and a compound represented by the following formulas (a3-3) and (a3-4) is more preferred.

In the above formula, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ²³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ^{22 is} preferably a single bond, a linear or branched alkyl group such as methylene, ethyl, propyl, tetramethylene, ethyl ethyl, methylene, Hexamethylene. As R ²³ , for example, a methyl group or an ethyl group is preferable.

(A2) the copolymer may also be further copolymerized as described above Other compounds outside. Examples of such other compounds include (meth)acrylates, (meth)acrylamides, allyl compounds, and the like. Vinyl ethers, vinyl esters, styrenes, and the like. These compounds may be used alone or in combination of two or more.

(meth)acrylates include (meth) Linear or branched (methyl) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, trioctyl (meth) acrylate, etc. ) alkyl acrylate; chloroethyl (meth) acrylate, 2,2-dimethyl hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (methyl) ) acrylate, benzyl (meth) acrylate, decyl (meth) acrylate, and the like.

Examples of (meth) acrylamides include (methyl) Acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl ( Methyl) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, and the like.

Examples of the allyl compound include allyl acetate and Allyl acrylate, allyl octylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetate, allyl lactate, etc. Base esters; allyloxyethanol and the like.

Examples of the vinyl ethers include hexyl vinyl ether and octyl Vinyl ether, mercapto 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, diethyl Aminoethyl vinyl ether, butylaminoethyl ethylene An alkyl vinyl ether such as an ether, a benzyl vinyl ether or a tetrahydrofurfuryl vinyl ether; a vinyl phenyl ether, a vinyl tolyl ether, a vinyl chlorophenyl ether, a vinyl-2,4- A vinyl aryl ether such as dichlorophenyl ether, vinyl naphthyl ether or vinyl decyl ether.

Examples of the vinyl esters include vinyl butyrate and isobutylene. Vinyl acetate, vinyl trimethyl acetate, vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl acetate Oxy ester, vinyl phenyl acetate, ethylene vinyl acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, tetrachlorobenzoic acid Vinyl ester, vinyl naphthate, and the like.

As the styrene, styrene; methylbenzene Alkene, dimethyl styrene, trimethylstyrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, Alkyl styrene such as benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, ethoxymethyl styrene; methoxy styrene, 4-methyl Alkoxystyrene such as oxy-3-methylstyrene or dimethoxystyrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromobenzene Halogenated styrene such as ethylene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene Wait.

The constituent unit derived from the above (a1) unsaturated carboxylic acid The ratio of the (A2) copolymer is preferably from 1 to 25% by mass, more preferably from 8 to 16 quality%. Moreover, the ratio of the constituent unit of the (a3) unsaturated compound containing an alicyclic group to the (A2) copolymer is preferably from 1 to 30% by mass, more preferably from 5 to 20% by mass.

Further, the above-mentioned (a2) contains an epoxy group-containing unsaturation The ratio of the constituent unit of the compound to the (A2) copolymer is preferably from 20 to 60% by mass, more preferably from 20 to 40% by mass.

(A2) Mass average molecular weight of the copolymer (Mw: gel The measured value of polystyrene in permeation chromatography (GPC). The same in the present specification) is preferably from 2,000 to 200,000, more preferably from 5,000 to 30,000. By the above range, it is easy to obtain a balance between the film forming ability of the photosensitive resin composition and the development performance after exposure.

(A2) copolymer can be polymerized by well-known radicals Legal to manufacture. That is, each compound and a well-known radical polymerization initiator can be produced by dissolving in a polymerization solvent, and heating and stirring.

Further, as the (A) alkali-soluble resin, it may be suitably A resin comprising (A3) a copolymer having at least a constituent unit derived from the above (a1) unsaturated carboxylic acid and a constituent unit having a site which may be polymerized with (B) a photopolymerizable monomer described later, or at least The constituent unit of the (a1) unsaturated carboxylic acid, the constituent unit derived from the above (a2) epoxy group-containing unsaturated compound, and the composition of a portion which may be polymerized with a photopolymerizable monomer (B) to be described later. Unit (A4) copolymer. (A) When the alkali-soluble resin contains the (A3) copolymer or the (A4) copolymer, the adhesion of the photosensitive resin composition to the substrate and the breaking strength of the photosensitive resin composition after curing can be improved.

(A3) copolymer and (A4) copolymer may further Polymerization of (meth)acrylates, (meth)acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes described as other compounds in connection with (A2) copolymer Wait.

Having a site that may be polymerized with (B) photopolymerizable monomer The constituent unit preferably has an ethylenically unsaturated group as a site which may be polymerized with (B) a photopolymerizable monomer. The (A3) copolymer can be prepared by reacting at least a part of the carboxyl group contained in the homopolymer of the (a1) unsaturated carboxylic acid with the (a2) epoxy group-containing unsaturated compound. Further, the (A4) copolymer may be an epoxy resin obtained from a copolymer having a constituent unit derived from the above (a1) unsaturated carboxylic acid and a constituent unit derived from the above (a2) epoxy group-containing unsaturated compound. At least a portion of the group is prepared by reacting with (a1) an unsaturated carboxylic acid.

(A3) mass average score of copolymer and (A4) copolymer The amount is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000. By the above range, it is easy to obtain a balance between the film forming ability of the photosensitive resin composition and the development performance after exposure.

Relative to the solid content of the photosensitive resin composition, (A) The content of the alkali-soluble resin is preferably from 30 to 90% by mass, more preferably from 45 to 75% by mass. By being in the above range, it is easy to obtain a balance of development properties.

Having a site that may be polymerized with (B) photopolymerizable monomer The constituent unit preferably has an ethylenically unsaturated group as a site which may be polymerized with (B) a photopolymerizable monomer. Copolymer (A2) can be obtained by a part of the epoxy group in the copolymer of the (a1) unsaturated carboxylic acid and the constituent unit derived from the (a2) epoxy group-containing unsaturated compound is reacted with the (a1) unsaturated carboxylic acid. modulation.

The mass average molecular weight of the copolymer (A2) is preferably 2000. ~50000, more preferably 5000~30000. By the above range, it is easy to obtain a balance between the film forming ability of the photosensitive resin composition and the development performance after exposure.

Relative to the solid content of the photosensitive resin composition, (A) The content of the alkali-soluble resin is preferably from 30 to 90% by mass, more preferably from 45 to 75% by mass. By being in the above range, it is easy to obtain a balance of development properties.

<(B) Photopolymerizable monomer>

As the (B) photopolymerizable monomer contained in the photosensitive resin composition of the present invention, a monomer having an ethylenically unsaturated group can be preferably used. Among the monomers having an ethylenically unsaturated group, there are monofunctional monomers and polyfunctional monomers.

As a monofunctional monomer, (meth) propylene oxime Amine, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) propylene oxime Amine, butoxymethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol (meth) acrylamide, (meth) acrylic acid, Fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citrate, citrate, crotonic acid, 2-propenylamine-2-methyl Propane sulfonic acid, tert-butyl propylene decyl 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-(meth)acrylate Phenoxy-2-hydroxypropyl ester, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate , dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2, 2, 3, 3 (meth) acrylate - a semi-(meth) acrylate such as tetrafluoropropyl ester or a phthalic acid derivative. These monofunctional single systems may be used singly or in combination of two.

On the other hand, examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol II. (Meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(a) Acrylate, trimethylolpropane tri(meth)acrylate, glycerol 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-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxyphenyl)propane, 2-hydroxy- 3-(Methyl)acryloxypropyl (meth) acrylate, ethylene glycol diepoxypropyl ether di(meth) acrylate, diethylene glycol bicyclo Propyl ether di(meth)acrylate, diepoxypropyl phthalate di(meth)acrylate, glycerol triacrylate, glycerol polyepoxypropyl ether poly(meth)acrylate, amine group Reaction of formate (meth) acrylate (ie, toluene diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate, sub a polyfunctional monomer such as methyl bis(methyl) acrylamide, (meth) acrylamide methyl ether, a condensate of a polyol and N-methylol (meth) acrylamide, or 1 ,3,5-tripropylene decyl hexahydro-1,3,5-three Wait. These polyfunctional single systems may be used alone or in combination of two or more.

Among these monomers having an ethylenically unsaturated group, In order to improve the adhesion of the photosensitive resin composition to the substrate and the strength after curing of the photosensitive resin composition, a trifunctional or higher polyfunctional monomer is preferred, and a six or more functional polyfunctional monomer is more preferred. body.

The content of the component (B) is preferably from 5 to 60% by mass, and more preferably from 10 to 50% by mass, based on the solid content of the photosensitive resin composition. By being in the above range, there is a tendency to easily obtain a balance between sensitivity, developability, and resolution.

<(C) Photopolymerization initiator>

The (C) photopolymerization initiator which is contained in the photosensitive resin composition of the present invention is not particularly limited, and a conventional 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-hydroxyethyl) Oxy)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)one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)-butan-1-one, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indole Zyrid-3-yl], 1-(O-acetamidine), (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methyl) Ethyloxy)-2-methylphenyl]methanone O-acetamidine, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidene)肟)], 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 4-benzylidene-4'-methyldimethyl sulfide, 4-dimethylaminobenzene Formic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethyl Hexyl benzoic acid, 4-dimethyl Amino-2-isopentylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethylketal, 1-phenyl-1,2-propanedione-2-(O- Ethoxycarbonyl) oxime, methyl o-benzoyl benzoate, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro- 4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylhydrazine, Octamethylguanidine, 1,2-benzopyrene, 2,3-diphenylanthracene, azobisisobutyronitrile, benzhydryl peroxide, cumene peroxide, 2-mercapto Benzimidazole, 2-mercaptobenzoene Azole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, diphenyl ketone, 2-chlorodiphenyl Ketone, p,p'-bisdimethylaminodiphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-dichlorodiphenyl ketone, 3,3 - dimethyl-4-methoxydiphenyl ketone, benzoin, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Phenylacetone, dichloroacetophenone, trichloroacetophenone, p-t-butylacetophenone, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p- Third butyl dichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzo Cycloheptanone, pentyl-4-dimethylaminobenzoate, 9-phenyl acridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9 -acridinyl)pentane, 1,3-bis-(9-acridinyl)propane, p-methoxy three , 2,4,6-tris(trichloromethyl)-s-three 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-three 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-three 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-three Wait. These photopolymerization initiators may be used alone or in combination of two or more.

Among them, in terms of sensitivity, it is particularly preferable to use a lanthanide photopolymerization initiator. Among the photopolymerization initiators of the lanthanide series, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl] is particularly preferred. , 1-(O-acetamidine), ethyl ketone, 1-[9-ethyl-6-(pyrrol-2-ylcarbonyl)-9H-carbazol-3-yl], 1-(O-acetamidine)肟), and 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzhydrylhydrazine)].

The content of the component (C) is preferably from 0.5 to 30% by mass, and more preferably from 1 to 20% by mass, based on the solid content of the photosensitive resin composition. By setting the content of the component (C) to the above range, a photosensitive resin composition having a pattern excellent in water resistance can be obtained.

Further, in the component (C), a photoinitiating aid may be combined. Examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl ketone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxy Base, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoene Oxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, pentaerythritol tetradecyl acetate, 3-mercaptopropionate, etc. a thiol compound or the like. These photoinitiating aids can be used individually or in combination of 2 or more types.

<(D) decane coupling agent>

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

R ¹ _m R ² _(3-m) Si-R ³ -NH-C(O)-YR ⁴ -X. . . (1) (In the formula (1), R ¹ is an alkoxy group, R ² is an alkyl group, m is an integer of 1 to 3, R ³ is an alkyl group, and Y is -NH-, -O- or -S - R ⁴ is a single bond or an alkylene group, X may have a substituent or a monocyclic or polycyclic nitrogen-containing heteroaryl group, and a -YR ⁴ -bonded ring nitrogen-containing 6 member in X An aromatic ring, a -YR ⁴ - is bonded to a carbon atom in the aforementioned nitrogen-containing 6-membered aromatic ring).

In the formula (1), R ¹ is an alkoxy group. The number of carbon atoms of R ¹ and alkoxy group is preferably from 1 to 6, more preferably from 1 to 4, and particularly preferably from 1 or 2 from the viewpoint of reactivity of the (D) decane coupling agent. Preferred examples of R ¹ include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a second butoxy group, and a third butoxy group. Base, n-pentyloxy and n-hexyloxy. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred.

The stanol group formed by the hydrolysis of R ^{1 of the} alkoxy group reacts with the surface of the substrate or the like to improve the adhesion of the pattern formed using the photosensitive resin composition to the surface of the substrate. Therefore, m is preferably 3 from the viewpoint of easily improving the adhesion of the pattern to the surface of the substrate.

In the formula (1), R ² is an alkyl group. The number of carbon atoms of the alkyl group in R ² is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 or 2 from the viewpoint of the reactivity of the (D) decane coupling agent. Preferable specific examples of R ² include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a n-pentyl group, and a n-hexyl group. , n-heptyl, n-octyl, n-decyl, n-decyl, n-decyl and n-decyl.

In the formula (1), R ³ is an alkyl group. With respect to R ³ , the number of carbon atoms of the alkyl group is preferably from 1 to 12, more preferably from 1 to 6, particularly preferably from 2 to 4. Preferred examples of R ³ include a methylene group, a 1,2-extended ethyl group, a 1,1-extended ethyl group, a propane-1,3-diyl group, and a propane-1,2-diyl group. Propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-diyl, butane -1,1-diyl, butane-2,2-diyl, butane-2,3-diyl, pentane-1,5-diyl, pentane-1,4-diyl, and Alkan-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,9-diyl, decane-1,10-diyl, ten Mono-n-l,11-diyl and dodecane-1,12-diyl. Among these alkylene groups, preferred are 1,2-extended ethyl, propane-1,3-diyl and butane-1,4-diyl.

Y is -NH-, -O- or -S-, preferably -NH-. Due to - The bond shown by -CO-O- or -CO-S- is more difficult to be hydrolyzed than the bond shown by -CO-S-, so if a compound containing Y is -NH- is used as ( D) A photosensitive resin composition of a decane coupling agent is likely to form a pattern excellent in water resistance.

R ⁴ is a single bond or an alkylene group, preferably a single bond. A preferred example when R ⁴ is an alkylene group is the same as R ³ .

X-system may have a monocyclic or polycyclic nitrogen-containing heteroaryl group having a substituent, and a -YR ⁴ -bonded ring-based nitrogen-containing 6-membered aromatic ring in X, -YR ⁴ - system and the nitrogen-containing The carbon atom in the 6-member aromatic ring is bonded. Although the reason is not known, when a photosensitive resin composition containing the compound of the X as the (D) decane coupling agent is used, it is possible to form a pattern excellent in adhesion to the substrate and water resistance.

When X is a polycyclic heteroaryl group, the heteroaryl group may be a plural single ring The group of condensation may also be a group in which a plurality of monocyclic rings 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 from 1 to 3. When X is a polycyclic heteroaryl group, the ring system of the nitrogen-containing 6-membered aromatic ring condensed or bound to X may or may not contain a hetero atom, and may be an aromatic ring or not an aromatic ring.

a substituent which may be possessed as X of the nitrogen-containing heteroaryl group, Examples thereof include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms. An aliphatic sulfhydryl group, a benzamidine group, a nitro group, a nitroso group, an amine group, a hydroxyl group, a thiol group, a cyano group, a sulfonic acid group, a carboxyl group, a halogen atom and the like. The number of the substituents which X has is not particularly limited as long as it does not impair the object of the present invention. The number of the substituents possessed by X is preferably 5 or less, more preferably 3 or less, and when X has a plural substituent, the plural substituents may be the same or different.

A preferred example of X is a group of the following formula.

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

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

Solid relative to the photosensitive resin composition excluding the colorant The content of the component (D) is preferably from 0.2 to 10% by mass, more preferably from 0.5 to 7% by mass. When the content of the component (D) is within the above range, the photosensitive resin composition can be used, and the pattern excellent in adhesion to the substrate and water resistance can be easily formed.

<(E) colorant>

The photosensitive resin composition of the present invention may further comprise (E) a colorant.

The (E) coloring agent contained in the photosensitive resin composition of the present invention is not particularly limited, and is classified into a pigment (Pigment), for example, in Color Index (CI; issued by The Society of Dyers and Colourists). The compound, specifically preferably, is a color index (CI) number as described below.

Examples of the yellow pigment which can be suitably used include CI Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same, 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 the orange pigment which can be suitably used include CI Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same, 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 the purple pigment which can be suitably used include CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" is the same, only the number is described), 19, 23, 29, 30, 32, 36, 37, 38, 39. 40 and 50.

As an example of a red pigment which can be suitably used, it can be mentioned CI Pigment Red 1 (hereinafter, "CI Pigment Red" is the same, 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, 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.

As an example of a blue pigment which can be suitably used, it can be mentioned C.I. Pigment Blue 1 (hereinafter, "C.I. Pigment Blue" is the same, only the number is described), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 66.

As the pigment of the above other hue which can be suitably used Examples thereof include green pigments such as CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 37, and Cu pigments such as CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, and CI Pigment Brown 28, and CI Pigment. Black pigment such as black 1, CI pigment black 7, and the like.

Further, when a coloring agent is used as the light shielding agent, the light shielding agent is preferably Use black or violet pigments. Examples of the black pigment or the violet pigment include metal oxides, composite oxides, and metals such as carbon black, anthraquinone pigment, titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver. Sulfides, metal sulfates, metal carbonates, etc., are not limited to various pigments of organic matter and inorganic matter. Among these, it is preferred to use carbon black having high light blocking properties.

As the carbon black, well-known carbon black such as channel black, furnace black, hot black, or lamp black can be used, and it is preferable to use a groove black having excellent light shielding properties. Further, carbon black may be coated with a resin.

Further, as the light shielding agent, an anthraquinone pigment is also preferable. Specific examples of the fluorene-based pigment include an anthraquinone-based pigment represented by the following formula (e-1), an anthraquinone-based pigment represented by the following formula (e-2), and the following formula (e-3); Shown lanthanide pigments. Among the commercially available products, product names K0084 and K0086, or pigment blacks 21, 30, 31, 32, 33, and 34 manufactured by BASF Corporation can be preferably used as the lanthanoid pigment.

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

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

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

The compound represented by the above formula (e-1) and the formula (e-2) are shown. The compound represented by the formula (e-3) can be synthesized, for example, by the method described in JP-A-621-1753 and JP-A-63-26784. That is, a heating reaction is carried out in water or an organic solvent using hydrazine-3,5,9,10-tetracarboxylic acid or a dianhydride thereof and an amine as a raw material. Then, the object obtained can be obtained by reprecipitating the obtained crude product in sulfuric acid or recrystallizing it in water, an organic solvent or a mixed solvent of these.

In order to make the lanthanide pigment good in the photosensitive resin composition The average particle diameter of the lanthanoid pigment is preferably from 10 to 1000 nm.

The sunscreen is used for the purpose of color tone modulation, etc. The black pigment or the purple pigment together may also contain a pigment such as red, blue, green or yellow. Pigments of other hue of black pigment or violet pigment are suitably selected from well-known pigments. For example, as the pigment of other hue of the black pigment or the violet pigment, various pigments described above can be used. The amount of the coloring matter of the color other than the black pigment or the violet pigment is preferably 15% by mass or less, and more preferably 10% by mass or less based on the total mass of the light-shielding agent.

In order to uniformly disperse the above colorant in the photosensitive resin A dispersant may be further used in the composition. As such a dispersing agent, a polyethyleneimine-based, urethane-based resin or acrylic resin-based polymer dispersing agent is preferably used. In particular, when carbon black is used as the colorant, an acrylic resin-based dispersant is preferably used as the dispersant.

In addition, inorganic pigments and organic pigments can be used individually or in combination When two or more kinds are used, the organic pigment is preferably used in an amount of from 10 to 80 parts by mass, more preferably from 20 to 40 parts by mass, per 100 parts by mass of the total of the inorganic pigment and the organic pigment. .

The amount of the coloring agent used in the photosensitive resin composition is The amount of the solid component of the photosensitive resin composition is preferably 100 parts by mass, preferably 5 to 70 parts by mass, more preferably 25 to 60 parts by mass, based on the total amount of the solid content of the photosensitive resin composition.

The colorant is preferably at a suitable concentration when a dispersant is used. After dispersing the dispersion, it is added to the photosensitive resin composition.

<(S) organic solvent>

In the photosensitive resin composition of the present invention, it is preferred to include (S) an organic solvent (hereinafter also referred to as "(S) component") for improvement in coatability or 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 Ethyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol single (poly)alkylene glycol monoalkyl ethers such as ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate (poly)alkylene glycol monoalkyl ether acetates such as diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate; Other ethers such as ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone, cyclohexanone, 2-heptanone, Ketones such as 3-heptanone; 2- Alkyl lactate such as methyl propyl propionate or ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, acetic acid B Ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyl Isopropyl acrylate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl acetate, ethyl 2-oxobutyrate, etc. Esters; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. . Among these, an alkanediol monoalkyl ether, an alkylene glycol monoalkyl ether acetate, an ether other than the above, an alkyl lactate, and an ester other than the above are preferable, and an alkane is more preferable. A diol monoalkyl ether acetate, an ether other than the above, and an ester other than the above. These solvents may be used alone or in combination of two or more.

The content of the (S) component is not particularly limited and may be The concentration applied to the substrate or the like is appropriately set in accordance with the thickness of the coating film. The viscosity of the photosensitive resin composition is preferably from 5 to 500 cp, more preferably from 10 to 50 cp, and particularly preferably from 20 to 30 cp. Further, the solid content concentration is preferably from 5 to 100% by mass, more preferably from 20 to 50% by mass.

<Other ingredients>

The photosensitive resin composition of the present invention may further contain an additive such as a surfactant, an adhesion improver, a thermal polymerization inhibitor, or an antifoaming agent as needed. Any of the additives can be used by conventional practitioners. Examples of the surfactant include compounds such as anionic, cationic, and nonionic. Examples of the adhesion improving agent include a conventional decane coupling agent, and examples of the thermal polymerization inhibitor include hydroquinone. Hydroquinone monoethyl ether, etc., as a defoaming agent, An anthracene oxygen type, a fluorine type compound, etc. are mentioned.

<Modulation Method of Photosensitive Resin Composition>

The photosensitive resin composition of the present invention may be mixed (dispersed, kneaded) with a mixer such as a three-roll mill, a ball mill, or a sand mill, and may be filtered by a filter such as a membrane filter of 5 μm as needed. modulation.

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 or a spin coater (rotary coating device) such as a roll coater, a reverse coater, or a bar coater, and curtain coating are used. In a non-contact type coating apparatus such as a machine, a photosensitive resin composition is applied onto a substrate to form a coating film.

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

Subsequently, the coating film on the substrate is selectively exposed by irradiation with an active energy ray such as ultraviolet rays or excimer laser light through a negative mask. The amount of energy rays to be irradiated also varies depending on the composition of the photosensitive resin composition, but is preferably, for example, about 30 to 2000 mJ/cm ² .

Selectively exposing the coated film by a developing solution To develop a pattern of the desired shape. The development method is not particularly limited, and for example, a dipping method, a spray method, or the like can be used. Examples of the developing solution include organic compounds such as monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts.

Secondly, for the pattern after development, 200 ° C ~ 250 ° C Left and right for post baking.

Using the photosensitive resin composition of the present invention, by the above The pattern formed by the method described above is excellent for adhesion to a substrate and water resistance, and is suitable for various uses. In particular, in the black matrix provided in various display devices represented by the liquid crystal display device, from the viewpoint of the reliability of the product, it is strongly required to be excellent in adhesion to the substrate and water resistance. Therefore, among the photosensitive resin compositions of the present invention, a pattern formed of a photosensitive resin composition containing a coloring agent containing a light-shielding agent is used as a black matrix.

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

[Examples]

In the examples, the following compounds 1 to 8 were used as the decane coupling agent. In the comparative examples, the following compounds 9 to 17 were used as the decane 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-t-butyl-4-methylphenol, and acrylic acid were placed in a 500 ml four-necked flask. 72.0 g, which was blown into the air at a rate of 25 ml/min, was heated and dissolved at 90 to 100 °C. Next, the solution was gradually heated while the solution became cloudy, and heated to 120 ° C to be completely dissolved. At this point, the solution gradually became transparent and viscous, but continued to stir as it did. The acid value was measured between the periods, and heating and stirring were continued until it became less than 1.0 mgKOH/g. It takes 12 hours for the acid price to reach the target value. Then, it was cooled to room temperature to obtain a bisphenolphthalein type epoxy acrylate represented by the following formula (a-4) which was colorless, transparent and solid.

Secondly, the above-mentioned bisphenol quinone type propylene-propylene thus obtained After adding 300 g of 3-methoxybutyl acetate to 307.0 g of the enoate to dissolve, 80.5 g of diphenyl ketone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised. The reaction was allowed to proceed at ~115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 ° C for 6 hours to obtain a resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectroscopy. In addition, this resin (A-1) corresponds to the resin represented by the above formula (a-1).

In Examples 11 to 18 and Comparative Examples 10 to 18, The resin (A-2) made of the units I to III shown below is used as an alkali-soluble resin. In the following formula, the number in the lower right of each unit means the content (% by mass) of each unit in the resin (A-2). The resin (A-2) had a mass average molecular weight of 7,000.

In the examples and the comparative examples, dipentaerythritol hexaacrylate (DPHA) was used as the photopolymerizable monomer.

In the 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 coloring For the agent, a carbon black dispersion liquid (CF black (manufactured by Royal Pharmaceutical Co., Ltd.) having a solid content concentration of 25% by mass) in which carbon black was dispersed in 3-methoxybutyl acetate was used.

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

100 parts by mass of the alkali-soluble resin (resin (A-1)), 35 parts by mass of the photopolymerizable monomer (DPHA), 15 parts by mass of the photopolymerization initiator, and 3 parts by mass of the decane coupling agent of the type described in Table 1. After 500 parts by mass of the carbon black dispersion, the mixture was diluted with an organic solvent to a solid concentration of 15% by mass to obtain a photosensitive resin composition. As a diluted organic solvent for the mixture, 3-methoxybutyl was used. A mixed solvent of a base acetate (MA), propylene glycol monomethyl ether acetate (PM) and cyclohexanone (AN) mixed with MA/PM/AN=60/20/20 (mass ratio). The obtained photosensitive resin composition was evaluated for fine line adhesion and water resistance in accordance with the following method.

(fine line adhesion evaluation)

The photosensitive resin composition was applied onto a glass substrate (100 mm × 100 mm) by a spin coater, and prebaked at 90 ° C for 120 seconds to form a coating film having a film thickness of 1.0 μm. Next, using a mirror projection alignment exposer (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 formed with a pattern having a width of 5 μm. . The exposure amount was 4 stages of 10, 20, 40, and 100 mJ/cm ² . The exposed coating film was developed for 50 seconds in a 0.04 mass% KOH aqueous solution at 26 ° C, and then post-baked at 230 ° C for 30 minutes to form a line pattern.

The fine line adhesion was evaluated by observing the line pattern formed by each exposure amount by an optical microscope. In the pattern formed, the case where the peeling from the substrate was not observed was judged as "good". A part or all of the formed pattern was peeled off from the substrate, and the pattern of the desired shape could not be formed as "poor". The judgment of the fine line adhesion of the photosensitive resin compositions of the respective Examples and Comparative Examples is shown in Table 1 for each exposure amount.

(water resistance evaluation)

A coating film having a film thickness of 1.0 μm was formed on the glass substrate in the same manner as the evaluation of the fine line adhesion. The formed coating film was exposed without exposure to a mask at an exposure amount of 100 mJ/cm ² to form a cured film on the glass substrate. The water resistance was evaluated using the formed cured film. The glass substrate having the cured film was placed in a pressure-resistant container at 120 ° C, 2 atm, and a humidity of 100% for 24 hours. At the time of 2 hours, 6 hours, 12 hours, and 24 hours, the glass substrate was taken out from the pressure resistant container, and it was observed whether or not the cured film was peeled off from the glass substrate. The case where the cured film was not peeled off from the glass substrate was judged to be "good". The case where the cured film was peeled off from the glass substrate was judged to be "poor".

[Examples 9 and 10]

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

It is understood from Tables 1 to 3 that the photosensitive solution containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator and a color former, and containing the compound represented by the above formula (1) as a decane coupling agent is used. The pattern formed by the resin composition allows a good pattern to adhere to the substrate and good water resistance.

On the other hand, as shown in Table 1 and Table 2, it is known to use an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a coloring agent, but The pattern formed by the photosensitive resin composition of the comparative example of the decane coupling agent was not contained in the compound represented by the above formula (1), and the adhesion of the favorable pattern to the substrate and the excellent water resistance could not be coherent.

In particular, it can be seen from Comparative Examples 6 to 8 regarding the photosensitive tree The decane coupling agent contained in the lipid composition is a pattern formed of a photosensitive resin composition when the hetero ring directly bonded to the -NH-CO-NH- group is a nitrogen-containing 5-membered ring, and is excellent in water resistance. Also, the fine line is poorly attached.

Further, as is understood from Comparative Example 9, the composition of the photosensitive resin In the decane coupling agent contained in the product, when the benzene ring is directly bonded to the -NH-CO-NH- group, the pattern formed using the photosensitive resin composition is inferior in fine line adhesion and slightly in water resistance.

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

58.5 parts by mass of the alkali-soluble resin (resin (A-2)), and 40 parts by mass of the photopolymerizable monomer (DPHA) and 1.5 parts by mass of the photopolymerization initiator, and the mass of the decane coupling agent of the type described in Table 2 After the mixture, the mixture was diluted with an organic solvent to a solid concentration of 15% by mass to obtain a photosensitive resin composition, and as an organic solvent for dilution of the mixture, diethylene glycol methyl ethyl ether (MEDG) and propylene glycol were used. Monomethyl ether acetate (PM) is a mixed solvent of MEDG/PM=60/40/(mass ratio). The fine line adhesion and water resistance of the obtained photosensitive resin composition were evaluated in the same manner as in Example 1.

It can be seen from Table 5 and Table 6 that if it is used, it contains alkali solubility. A pattern formed by the resin, the photopolymerizable monomer and the photopolymerization initiator, and the compound represented by the above formula (1) as a photosensitive resin composition of the example of the decane coupling agent can provide a good pattern. The adhesion of the type to the substrate coexists with good water resistance.

On the other hand, as shown in Tables 5 and 6, the use of alkali is used. The soluble resin, the photopolymerizable monomer, and the photopolymerization initiator are not included in the pattern formed by the photosensitive resin composition of the comparative example of the decane coupling agent, and the compound represented by the above formula (1) is not good. The pattern adheres to the adhesion of the substrate and good water resistance.

In particular, as can be seen from Comparative Examples 15 to 18, regarding photosensitivity The decane coupling agent contained in the resin composition is a pattern formed of a photosensitive resin composition when the ring directly bonded to the -NH-CO-NH- group is a nitrogen-containing 5-membered ring or a benzene ring, and is resistant to water. Excellent in sex and poor in fine line.

Claims (6)

A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a decane coupling agent, and the (D) decane coupling agent a compound represented by the following formula (1); R ¹ _m R ² _(3-m) Si-R ³ -NH-C(O)-YR ⁴ -X‧‧‧(1) In the formula (1), R ¹ is an alkoxy group, R ² is an alkyl group, m is an integer of 1 to 3, R ³ is an alkylene group, Y is a -NH-, R ⁴ single bond, and the X system may have a substituent and may be a single ring. Or a polycyclic nitrogen-containing heteroaryl group, the ring of -YR ⁴ -bonded in X is a nitrogen-containing 6-membered aromatic ring, and the -YR ⁴ - is bonded to a carbon atom in the aforementioned nitrogen-containing 6-membered aromatic ring. The photosensitive resin composition of claim 1, which further contains (E) a colorant. The photosensitive resin composition of claim 2, wherein the (E) colorant is an opacifier. A method for forming a pattern, comprising the steps of: applying a photosensitive resin composition according to any one of claims 1 to 3 to a substrate to form a coating film, and selectively exposing the coating film to a position And a step of developing the exposed coating film to be exposed. A black matrix formed using the photosensitive resin composition of claim 3. A display device having a black matrix as in claim 5.