TWI590000B - Photosensitive composition - Google Patents

Description

Photosensitive composition

The present invention relates to a photosensitive composition containing a decane coupling agent composed of blocked isocyanate decane, a colored photosensitive composition containing a coloring agent to the photosensitive composition, and a black matrix using the colored photosensitive composition. Specifically, it relates to a color-sensitive photosensitive composition superior in adhesion to a substrate and a black matrix using the same.

The photosensitive resin composition is a photocurable resin composition, and examples of the composition include a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since the photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, it can be used for photocurable inks, photosensitive printing plates, printed wiring boards, various photoresists, and the like.

In particular, the pigment is a colored photosensitive resin composition using carbon black, which is suitable as a boundary between the color layers of R, G, and B which are provided in a color filter for improving display contrast or color development. Part of the black matrix.

A black pattern (black matrix) obtained by exposure, development, and post-hardening of such a color-sensitive photosensitive composition, which is transparent The adhesion of the substrate is insufficient, and in the peeling step of forming the black pattern repeatedly, one part of the color pattern formed first is peeled off at the same time, the pattern is peeled off, and the exposure hardened portion does not remain on the transparent substrate. The problem.

Patent Document 1 discloses a compound having a functional group which is a functional group which is chemically bonded to a transparent substrate and a functional group which is a component of the photosensitive coloring material. A polymerizable functional group; in particular, a photosensitive coloring material for forming a colored pixel pattern containing a decane coupling agent.

Further, Patent Documents 2 to 4 disclose a decane coupling agent composed of a blocked isocyanate decane having a specific structure.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-191724

[Patent Document 2] Japanese Patent Publication No. 08-291186

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-067787

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-144255

However, the invention described in Patent Document 1 is limited to a pattern-former who uses dry development of a dry film, and has a space for improvement in adhesion to a substrate. Also, in Patent Documents 2 to 4 There is no description or teaching, and the decane coupling agent described in the literature is used for the photosensitive resin composition.

Accordingly, an object of the present invention is to provide a coloring photosensitive composition which can form a desired pattern and a coloring pattern which is improved in adhesion to a substrate.

In order to solve the above problems, the inventors of the present invention have found that a photosensitive composition containing a decane coupling agent composed of a specific blocked isocyanate decane can achieve the above object, and it is known that The colored photosensitive composition in which a coloring agent is added to the photosensitive composition is suitable for a black matrix, and the present invention has been completed.

In other words, the photosensitive composition of the present invention contains a decane coupling agent composed of a blocked isocyanate decane, and the blocked isocyanate decane is an isocyanate compound represented by the following formula (I) and a blocking agent. The person who got the reaction,

(wherein R ¹ is represented by an alkyl group having 1 to 8 carbon atoms, n is a number from 1 to 10, a is a number from 1 to 3, b is a number from 0 to 2, and a + b = 3).

Further, the colored photosensitive composition of the present invention is characterized in that a coloring agent is added to the photosensitive composition.

The photosensitive composition and the coloring photosensitive composition of the present invention preferably contain a polymerizable compound having an ethylenically unsaturated bond, and Photopolymerization initiator.

Further, the colored photosensitive composition of the present invention preferably contains a black pigment.

Moreover, the photosensitive composition of the present invention and the coloring photosensitive composition are preferably alkali developability.

Further, in the photosensitive composition of the present invention and the colored photosensitive composition, it is preferred that the blocking agent is an anthracene compound.

The black matrix of the present invention is characterized in that the colored photosensitive composition is cured on a substrate.

The color filter of the present invention is characterized by comprising the above-described black matrix.

According to the present invention, it is possible to provide a photosensitive composition which can form a desired pattern, and a coloring photosensitive composition which can improve the adhesion to a substrate of a colored pattern, and a black matrix using the same. The cured product of the colored photosensitive composition of the present invention is suitable for a color filter for a display device, a liquid crystal display panel, and an organic EL display panel.

[Best Mode for Carrying Out the Invention]

Hereinafter, the photosensitive composition of the present invention and the coloring photosensitive composition will be described based on preferred embodiments.

The photosensitive composition of the present invention contains a reaction obtained by reacting an isocyanate compound represented by the above formula (I) with a blocking agent. To the blocked isocyanate decane. The polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, or the like is suitable as the other component, but is not limited thereto.

Further, the colored photosensitive composition of the present invention is a coloring agent added to the photosensitive composition of the present invention. As the colorant, a black pigment containing carbon black or the like is preferable. It is suitable as a photosensitive composition for forming a black matrix by containing a black pigment. Further, since development can be carried out without causing a load on the environment, alkali developability is preferred.

The alkyl group having 1 to 8 carbon atoms represented by R ^{1 of the} above formula (I) may, for example, be methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl or tert-butyl. Base, iso-butyl, pentyl, iso-pentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3- Heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl and the like.

In the above formula (I), R ^{1 is} preferably a methyl group, an ethyl group or a propyl group in terms of the ease of obtaining the raw material.

Further, n is preferably 2 to 4 in terms of the boiling point. The boiling point is preferably higher than the prebaking temperature or the post-baking temperature.

Further, in terms of the adhesion, a is preferably 3, and b is preferably 0.

As a blocking agent for obtaining the blocked isocyanate decane used in the present invention, a conventional user can be used. Examples thereof include carboxylates such as dimethyl malonate and diethyl malonate; malonic acid, acetamidineacetone, and ethyl acetate (ethyl acetate, ethyl acetate, etc.). Active methylene compound; methotrexate, acetophenone, acetone oxime , diethyl hydrazine, diphenyl ketone oxime, cyclohexanone oxime, methyl ethyl ketone oxime (MEK 肟), methyl isobutyl ketone oxime (MIBK 肟), dimethyl ketone oxime, diethyl An oxime compound such as ketone oxime; methanol, ethanol, propanol, butanol, 2-ethylhexanol, heptanol, hexanol, octanol, isodecyl alcohol, stearyl alcohol, benzyl alcohol, etc. Isomers; methylglycol, ethylene glycol, ethyl diglycol, ethyl triethylene glycol, butanol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol Glycol derivatives such as ethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether; phenol, cresol, xylenol, ethyl phenol, propyl phenol, butyl phenol, octyl phenol, hydrazine a phenol such as a phenol, a nitrophenol or a chlorophenol or an isomer thereof: a hydroxyl group-containing ester such as methyl lactate or amyl lactate; dibutylamine, diisopropylamine, di-tert - amine compounds such as butylamine, di-2-ethylhexylamine, dicyclohexylamine, benzylamine, diphenylamine, aniline, carbazole, etc.; sub-ethylenimine, polyethylenimine, etc. Amine compound; monomethylethanolamine, diethylethanolamine, triethyl Alcoholamines such as ethanolamine; snails such as α-pyrrolidone, β-butyrolactam, β-propionamide, γ-butyrolactam, δ-valeroinamide, ε-caprolactam, etc. Amines; thiols such as butyl mercaptan, hexyl mercaptan, lauryl mercaptan; imidazoles such as imidazole and 2-ethylimidazole; acetophenone, acrylamide, acetamide, dimer acid amine Such as guanamines; succinimides such as butylenediamine, maleic imine, phthalimide, urea compounds such as urea, thiourea, ethylene urea, etc.; benzotriazoles; Pyrazoles such as 3,5-dimethylpyrazole. These may be used alone or in combination of two or more.

Among the above blocking agents, the dissociation temperature is 100 to 200 ° C, which is stable during prebaking, and is the point at which the reaction is carried out after post baking. Good, among them, bismuth compounds are preferred.

The blocking reaction for obtaining the blocked isocyanate decane can be carried out by a known reaction method. The amount of the blocking agent to be added is usually from 1 to 2 equivalents, preferably from 1.05 to 1.5 equivalents, per equivalent of the isocyanate group.

The reaction temperature of the blocking reaction is usually 50 to 150 ° C, preferably 60 to 120 ° C. The reaction time is preferably about 1 to 7 hours. Further, a catalyst or a solvent (an aromatic hydrocarbon, an ester system, an ether system, a ketone system, or a mixed solvent of two or more kinds thereof) may be added.

In the photosensitive composition of the present invention, the content of the decane coupling agent is 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass, based on the solid content of the photosensitive composition of the present invention. When the content of the decane coupling agent is less than 0.1% by mass, the adhesion may be insufficient. When the amount is 30% by mass, the decane coupling agent may be precipitated in the photosensitive composition.

As the photosensitive composition of the present invention, a polymerizable compound having an ethylenically unsaturated bond can be used. The polymerizable compound having the ethylenically unsaturated bond is not particularly limited, and those conventionally used for the photosensitive composition may, for example, be ethylene, propylene, butylene, isobutylene, vinyl chloride or vinylidene chloride. Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, humic acid, Butenoic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid single [2-(Methyl)propenyloxyethyl]ester, ω-carboxypolycaprolactone mono(meth)acrylate, etc., mono(meth)acrylate having a polymer of a carboxyl group and a hydroxyl group at both terminals ; hydroxyethyl (meth) acrylate. Maleate, hydroxypropyl (meth) acrylate. Maleate, dicyclopentadiene. An unsaturated polybasic acid such as a maleic acid ester or a polyfunctional (meth) acrylate having one or more carboxyl groups and two or more (meth) acrylonitrile groups; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, the following compounds No. A1 to No. A4, methyl (meth)acrylate, butyl (meth)acrylate, (A) Isobutyl acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (methyl) Isodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, (methyl) Dimethylaminoethyl acrylate, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, (meth) acrylate poly ( Ethoxy)ethyl ester, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid vinyl ester, (meth)acrylic acid Propyl ester, benzyl (meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol Di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trishydroxyl Ethylene tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(methyl) Acrylate, pentaerythritol tri(meth)acrylate, tricyclodecane hydroxymethyl di(meth) acrylate, tris[(meth) propylene decylethyl]isocyanurate, polyester (methyl ) an unsaturated monobasic acid such as an acrylate oligomer and an ester of a polyhydric or polyhydric phenol; a metal salt of an unsaturated polybasic acid such as zinc (meth) acrylate or magnesium (meth) acrylate; maleic anhydride; Anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3 -methyl- Unsaturated polybasic acid such as 3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride, methyl humic anhydride Anhydride; (meth) acrylamide, methylene bis-(meth) acrylamide, diethylene triamine tri (meth) acrylamide, benzyl bis (meth) acrylamide, An unsaturated monobasic acid such as α-chloropropenylamine or N-2-hydroxyethyl(meth)acrylamide or a polyamine of a polyvalent amine; an unsaturated aldehyde such as acrolein; (meth)acrylonitrile; Unsaturated nitrile such as α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide, etc.; styrene, 4-methylstyrene, 4-ethylstyrene, 4 -methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinyl An unsaturated aromatic compound such as benzyl methyl ether or vinylbenzyl glycidyl ether; an unsaturated ketone such as methyl vinyl ketone; vinylamine, allylamine, N-vinylpyrrolidone or vinylpiperidine Wait no And amine compounds; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl groups such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether Ether; unsaturated quinone imines such as maleic imine, N-phenylmaleimide, N-cyclohexylmaleimide; anthracene such as hydrazine or 1-methylhydrazine; Aliphatic conjugated dienes of butadiene, isoprene, chloropentadiene, etc.; polystyrene, poly(methyl) methacrylate, poly(meth) acrylate, n-oxygen An alkane or the like, a macromonomer having a mono(meth)acrylonitrile group at the end of a polymer molecular chain; vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate , triallyl isocyanurate, vinyl sulfide, vinyl imidazole, vinyl Ethylene with azole, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, vinyl monomer containing hydroxyl group and polyisocyanate compound, vinyl monomer containing hydroxyl group and polyepoxide Epoxy compound.

Further, as the polymerizable compound having an ethylenically unsaturated bond, a copolymer of acrylate or a phenol and/or a cresol novolac epoxy resin; a polyphenylmethane ring having a polyfunctional epoxy group may be used. Oxygen resin; epoxy acrylate resin; a resin obtained by reacting an epoxy compound such as an epoxy compound represented by the following formula (II) with an unsaturated monobasic acid and further reacting with a polybasic acid anhydride. In the above, a resin obtained by reacting an epoxy compound such as an epoxy compound represented by the following formula (II) with an unsaturated monobasic acid and further reacting with a polybasic acid anhydride is preferred. Further, it is preferred that these compounds contain 0.2 to 1.0 equivalent of an unsaturated group.

(wherein X ¹ represents a direct bond, a methylene group, an alkylene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO ₂ , SS, SO, CO Or OCO or a substituent represented by the following formula (i), (ii) or (iii), wherein the above alkylene group may be substituted by a halogen atom, and R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom; An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or a halogen atom, and the above alkyl group, alkoxy group and alkenyl group may pass through a halogen atom Instead, m is an integer from 0 to 10, and the optical isomer present when m is not 0 may be any isomer).

(wherein Z ¹ represents a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms which is substituted by an alkoxy group having 1 to 10 carbon atoms, and Y ¹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a carbon number. An alkenyl group or a halogen atom of 2 to 10, the above alkyl group, alkoxy group and alkenyl group may be substituted by a halogen atom, and b is an integer of 0 to 5).

(wherein Y ² and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, and may be substituted by a halogen atom; An aryloxy group having 6 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms which may be substituted by a halogen atom, an aralkenyl group having 6 to 20 carbon atoms which may be substituted by a halogen atom, may be substituted by a halogen atom An aralkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms which may be substituted by a halogen atom, or a halogen atom, and an alkyl group in the above alkyl group and aralkyl group may be Saturated bond, -O- or -S-interrupt, Z ² can form a ring with adjacent Z ² , p represents an integer from 0 to 4, q represents an integer from 0 to 8, r represents an integer from 0 to 4, and s represents An integer from 0 to 4, the total number of r and s is an integer from 2 to 4.

Examples of the unsaturated monobasic acid which acts on the above epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and hydroxyethyl methacrylate. Maleate, hydroxyethyl acrylate. Maleic acid ester, hydroxypropyl methacrylate. Maleic acid ester, hydroxypropyl acrylate. Maleate, dicyclopentadiene. Maleic acid ester and the like.

Further, after the action of the above unsaturated monobasic acid, examples of the polybasic acid anhydride which acts further include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, and biphthalic acid dianhydride (biphthalic). Anhydride), maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-diphenyl ketone tetracarboxylic anhydride, ethylene glycol trimellitate, glycerol Pyromellitic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ceric anhydride, methylic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydroortylene Methyl anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-butylene A dianhydride adduct, dodecenyl succinic anhydride, methyl humic anhydride, and the like.

The above epoxy compound, the above unsaturated monobasic acid, and The reaction molar ratio of the polybasic acid anhydride is preferably as follows.

In other words, in the epoxy adduct having a structure in which 0.1 to 1.0 of the carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the polybasic acid anhydride is preferably used. The acid anhydride structure is in a ratio of 0.1 to 1.0 with respect to one hydroxyl group of the epoxy adduct.

The reaction of the above epoxy compound, the above unsaturated monobasic acid, and the above polybasic acid anhydride can be carried out according to a usual method.

As the polymerizable compound having an ethylenically unsaturated bond, a polymer represented by the following formula (III) can also be used.

(wherein X ₁₁ represents a hydrogen atom or a methyl group, Y ₁₁ represents a divalent linking group, R ₁₁ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a carbon number of 7 to 20 The aralkyl group, the alkyl group, the aryl group and the aralkyl group, may be substituted by a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group and the aralkyl group may be -O-, -S-, - CO-, -COO-, -OCO- or -NH-, or a combination of these linkages to interrupt, R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom or a carbon atom, 0.1 ≦t ≦ 0.65, 0.3 ≦m≦0.8, 0≦n≦0.2, t+m+n=1).

The divalent linking group represented by Y ₁₁ in the above formula (III) is a structure represented by the following formula (1).

(wherein X ¹¹ represents -CR ²⁰ R ²¹ -, -NR ²⁰ -, a chain hydrocarbon group having a divalent carbon number of 1 to 35, an alicyclic hydrocarbon group having a divalent carbon number of 3 to 35, and a divalent carbon atom; a 6 to 35 aromatic hydrocarbon group or a divalent carbon group having 2 to 35 carbon atoms, or a combination of these groups; R ²⁰ and R ²¹ represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms; a group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and Z ¹¹ and Z ¹² each independently represent a direct bond, -O-, -S-, -SO ₂ -, -SO -, -NR ¹⁰ -, -PR ¹⁰ -, R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. Alkyl, aryl and aralkyl groups may be substituted by a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group and the aralkyl group may be -O-, -S-, -CO-, -COO- And -OCO- or -NH-, or a combination of these linkage groups, is interrupted. However, the group represented by the above formula (1) is in the range of 1 to 35 carbon atoms.

Among the polymerizable compounds having an ethylenically unsaturated bond, when a compound having an acid value is used, the photosensitive composition of the present invention can be provided with alkali developability. When the compound having an acid value is used, the amount thereof is preferably from 50 to 99% by mass based on the entire polymerizable compound having an ethylenically unsaturated bond.

Further, the above-mentioned compound having an acid value can be further controlled by a monofunctional Or a polyfunctional epoxy compound is reacted to adjust the acid value and then used. The alkali developability of the photosensitive resin can be improved by adjusting the acid value of the above-mentioned acid-valent compound. The above-mentioned compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability), the acid value of the solid matter is preferably in the range of 5 to 120 mgKOH/g, and the monofunctional or polyfunctional epoxy compound is preferred. The amount of use is preferably selected in such a manner as to satisfy the above-mentioned acid value.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, and the like. Butyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-B Hexyl hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butyl Phenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-mercaptophenyl glycidyl ether, benzyl glycidyl ether, p-isopropylphenyl phenyl glycidol Ether, trityl glycidyl ether, methacrylic acid 2,3-epoxypropyl ester, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane A styrene oxide, a decene oxide, a methyl styrene oxide, an epoxycyclohexane, a propylene oxide, and the said compound are No. A2, No. A3, etc..

When one or more compounds selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers are used as the polyfunctional epoxy compound, a coloring photosensitive resin composition having better characteristics can be obtained, and thus it is preferable. .

As the bisphenol type epoxy compound, in addition to the epoxy compound represented by the above formula (II), a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can be used.

Further, as the glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, or the like can be used. 1,8-octanediol diglycidyl ether, 1,10-nonanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether , triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexane dimethanol diglycidyl ether, 1,1,1-three (shrinkage Glyceryloxymethyl)propane, 1,1,1-tris(glycidoxymethyl)ethane, 1,1,1-tris(glycidoxymethyl)methane, 1,1,1,1 - Tetra(glycidoxymethyl)methane or the like.

Further, a phenolic novolac type epoxy compound, a biphenol novolak type epoxy compound, a cresol novolac type epoxy compound, a bisphenol A novolac type epoxy compound, a dicyclopentadiene novolac type epoxy compound, or the like may be used. Epoxy compound; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexyl An alicyclic epoxy compound such as a 3-,4-epoxycyclohexanecarboxylate or 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, four Hydrogen phthalic acid diglycidyl Glycidyl esters such as esters, glycidyl dimerates, glycidyl groups such as tetraglycidyldiaminediphenylmethane, triglycidyl-aminophenol, N,N-diglycidylaniline, etc. a heterocyclic epoxy compound such as an amine; 1,3-diglycidyl-5,5-dimethylhydantoin or triglycidyl isocyanurate; a dicyclopentadiene dioxide or the like a dioxide compound; a naphthalene type epoxy compound; a triphenylmethane type epoxy compound; a dicyclopentadiene type epoxy compound.

Further, the photosensitive composition of the present invention may contain a compound capable of imparting alkali developability without an ethylenically unsaturated bond, and as such a compound, any compound having an acid value and being soluble in an aqueous alkali solution may be used. Although not particularly limited, an alkali-soluble phenol resin (hereinafter simply referred to as "phenolic resin") can be exemplified as a representative. The phenolic resin is obtained by polycondensation of a phenol and an aldehyde in the presence of an acid catalyst.

As the phenol, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, or the like can be used. M-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-dimethyl Phenol, 2,3,5-trimethylphenol, p-phenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, benzenetriol, α-naphthol, bisphenol A , dihydroxybenzoic acid ester, gallic acid ester, etc.; among these phenols, preferred are phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3, 5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A. These phenols may be used alone or in combination of two or more.

As the above aldehyde, for example, formaldehyde or trimeric can be used. Aldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzene Formaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde , p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, etc.; among these compounds, formaldehyde, acetaldehyde and benzaldehyde are preferred. These aldehydes can be used alone or in combination of two or more. The aldehyde is preferably used in an amount of 0.7 to 3 moles, particularly preferably 0.7 to 2 moles, per 1 mole of phenol.

As the acid catalyst, for example, an inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid, or an organic acid such as formic acid, citric acid or acetic acid can be used. The amount of such an acid catalyst to be used is preferably from 1 × 10 ^-4 to 5 × 10 ^-1 mol per 1 mol of phenol. In the condensation reaction, water is usually used as the reaction medium. However, when the phenol used in the condensation reaction is not dissolved in the aqueous solution of the aldehyde, and the heterogeneous system is used from the initial stage of the reaction, the hydrophilic material may be used as the reaction medium. Solvent. Examples of such a hydrophilic solvent include alcohols such as methanol, ethanol, propanol, and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of the reaction medium used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. The reaction temperature of the condensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw material, but it is usually 10 to 200 ° C, preferably 70 to 150 ° C. After the end of the condensation reaction, in order to remove the unreacted raw materials, the acid catalyst and the reaction medium present in the system, the internal temperature is usually raised to 130 to 230 ° C, and the volatiles are fractionated under reduced pressure, followed by melting. The phenolic resin flows onto a steel conveyor belt or the like and is recovered.

Further, after the condensation reaction is completed, the reaction mixture is dissolved in the hydrophilic solvent, and a precipitant such as water, n-hexane or n-heptane is added to precipitate the phenol resin to separate the precipitate. It can also be recovered by heating and drying.

In addition to the above-mentioned phenol resin, examples of the compound capable of imparting alkali developability without an ethylenically unsaturated bond may, for example, be polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, or a poly Vinyl hydroxybenzoate and the like.

As the photosensitive composition of the present invention, a photopolymerization initiator can be used. As such a photopolymerization initiator, a conventionally known compound can be used, and examples thereof include diphenyl ketone, benzophenone, 1-hydroxy-1-benzhydrylcyclohexane, benzoin, and benzyldimethyl group. Ketone, 1-benzyl-1-dimethylamino-1-(4'- Phenylbenzimidyl)propane, 2-morpholinyl-2-(4'-methylindenyl) benzhydrazine, thioxanthone, 1-chloro-4-propoxythioxanthone, Isopropyl thioxanthone, diethyl thioxanthone, ethyl hydrazine, 4-benzylidene-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzamide Propane, 2-hydroxy-2-(4'-isopropyl)benzimidazole, 4-butylbenzhydryltrichloromethane, 4-phenoxybenzhydryldichloromethane, benzamidinecarboxylic acid Methyl ester, 1,7-bis(9'-acridinyl)heptane, 9-n-butyl-3,6-bis (2'- Olinoisobutyl) carbazole, 2-methyl-4,6-bis(trichloromethyl)-s-three 2-Benzene-4,6-bis(trichloromethyl)-s-three 2-naphthalene-4,6-bis(trichloromethyl)-s-three , 2,2-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine , camphor sputum, benzammonium peroxide, etc.; as a commercial product, for example, N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (made by ADEKA) ), IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF Co., Ltd.), and the like.

In the photosensitive composition of the present invention, the content of the photopolymerization initiator is from 0.1 to 30% by mass, particularly preferably from 0.5 to 10% by mass, based on the photosensitive composition of the present invention. When the content of the photopolymerization initiator is less than 0.1% by mass, the curing by exposure is insufficient; if 30% by mass is large, the initiator is precipitated in the photosensitive composition. .

Further, a coloring agent may be further added to the photosensitive composition of the present invention to form a coloring photosensitive composition. As the coloring agent, for example, an inorganic coloring material or an organic coloring material can be mentioned. These coloring materials may be used alone or in combination of two or more.

As the inorganic coloring material and the organic coloring material, for example, a nitroso compound, a nitro compound, an azo compound, a disazo compound, a dibenzopyran compound, a quinoline compound, an anthraquinone compound, or a coumarin compound can be used. , indigo compound, isoindolinone compound, isoporphyrin compound, quinophthalone compound, anthanthrone compound, purple ring ketone compound, hydrazine compound, diketopyrrolopyrrole compound, sulfur Indigo compound, dioxazine compound, triphenylmethane compound, quinoline yellow compound, naphthalenetetracarboxylic acid; metal complex of azo dye, flower blue dye; lake pigment; by furnace method, channel method, thermal cracking Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; if the carbon black is adjusted and coated with an epoxy resin, the carbon black is previously dispersed in a solvent with a resin. When the resin of 20~200mg/g is adsorbed, the carbon black is treated as an acidic or alkaline surface, and the average particle diameter is 8 nm or more and the DBP oil absorption is 90 ml/100 g or less, and the volatile matter from 950 ° C is used. CO in The calculated total oxygen amount of CO ₂ to carbon black surface area per 100m 9mg ² more; graphite, graphite carbon black, activated carbon, carbon fibers, carbon nanotubes, micro spiral carbon fibers, carbon nano horn, carbon Aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chrome oxide green, milorie blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate blue, Iron blue, ultramarine, ceruleanblue, chrome green, emerald green, lead sulfate, lead yellow, zinc yellow, red iron (red iron oxide (III)), cadmium red, synthetic iron black, brown soil Inorganic or organic pigments.

As the inorganic coloring material and the organic coloring material, commercially available pigments may be used, and examples thereof include: Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; pigment green 7, 10, 36; pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.

As the inorganic coloring material and the organic coloring material, a well-known dye can also be used. As known dyes, for example, azo dyes, anthraquinone dyes, anthraquinone dyes, triarylmethane dyes, dibenzopyran dyes, alizarin dyes, acridines, anthraquinone dyes, thiazole dyes, naphthol dyes, Quinoline dye, nitro dye, indamine dye, Dyes such as dyes, indigo dyes, and blue dyes.

In the coloring photosensitive composition of the present invention, the content of the coloring agent is preferably 0 to 350 parts by mass, more preferably 0 to 250, per 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. Parts by mass. When the amount is more than 350 parts by mass, the cured product of the colored photosensitive composition of the present invention is used, and since the light transmittance of the color filter for a display device is lowered and the luminance of the display device is lowered, it is not preferable.

Further, a solvent may be further added to the photosensitive composition of the present invention and the colored photosensitive composition. The solvent is usually a solvent which can dissolve or disperse the above components (the blocked isocyanate decane of the present invention, etc.) as needed, and examples thereof include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, and acetone. a ketone such as methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone or 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 An ether solvent such as 2-diethoxyethane or dipropylene glycol dimethyl ether; Ester ester solvent of methyl acetate, ethyl acetate, -n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc.; Alcohol monomethyl ether, ethylene glycol monoethyl ether, etc.; an alcoholic solvent such as methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol or pentanol; Glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methyl An ether ester solvent such as oxybutyl acetate or ethoxyethyl propionate; a BTX solvent such as benzene, toluene or xylene; or an aliphatic hydrocarbon such as hexane, heptane, octane or cyclohexane. a solvent; a terpene oil such as turpentine, D-limonene or decene; a paraffinic solvent such as mineral spirits, SWAZOL #310 (COSMO Matsuyama Petroleum Co., Ltd.), SOLVESSO #100 (EXXON Chemical Co., Ltd.); a halogenated aliphatic hydrocarbon solvent such as carbon tetrachloride, chloroform, trichloroethylene, dichloromethane or 1,2-dichloroethane; a halogenated aromatic hydrocarbon solvent such as chlorobenzene; carbitol Solvent, benzene , triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl azine, One type of these solvents may be used alone or two or more types may be used in combination. Among these, a ketone or an ether ester solvent, particularly propylene glycol-1-monomethyl ether-2-acetate or cyclohexanone, is used, and the photosensitive composition has an ethylenically unsaturated bond. In the case of a polymerizable compound, it is preferred that the compound having the ethylenically unsaturated bond has good compatibility with a photopolymerization initiator.

In the photosensitive composition of the present invention, the amount of the solvent used is determined by the concentration of the composition other than the solvent (solid matter). 5 to 30% by mass is preferred. When it is less than 5% by mass, it is difficult to make the film thickness thick, and it is difficult to sufficiently absorb the light of a desired wavelength. When it exceeds 30% by mass, the storage of the composition is lowered due to precipitation of the photosensitive component. Sex, or viscosity increases and the operability is reduced, so it is not suitable.

The photosensitive composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, cerium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, cerium oxide, and aluminum oxide; layered clay minerals; Milose blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum citrate, calcium citrate, Aluminum hydroxide, platinum, gold, silver, copper, and the like. Among these, titanium oxide, cerium oxide, layered clay mineral, silver, and the like are preferable. In the photosensitive composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. . These inorganic compounds may be used alone or in combination of two or more.

The photosensitive composition of the present invention contains an inorganic compound and can be used as a photosensitive paste composition. The photosensitive paste composition is a burn-in pattern for forming a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel. These inorganic compounds are also suitable as, for example, fillers, antireflective agents, conductive agents, stabilizers, flame retardants, mechanical strength enhancers, special wavelength absorbers, inks Agents, etc. are used.

When a coloring material such as a pigment or an inorganic compound is used in the coloring photosensitive composition of the present invention, a dispersing agent can be added. The dispersing agent is not limited as long as it can disperse and stabilize the coloring material or the inorganic compound, and a commercially available dispersing agent such as BYKCHEMIE, BYK series or the like can be used, and a polyester having a basic functional group is suitably used. a polyether or a polymer dispersant composed of a polyurethane having a nitrogen atom as a basic functional group, a functional group having a nitrogen atom as an amine and/or a quaternary salt thereof, and an amine value of 1~ 100mgKOH/g.

Further, in the photosensitive composition of the present invention, p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenolthiophene may be added as needed. Isothermal polymerization inhibitor; plasticizer; subsequent accelerator; filler; antifoaming agent; leveling agent; surface conditioner; antioxidant; ultraviolet absorber; dispersing aid; anti-agglomerating agent; catalyst; Conventional additives such as cross-linking agents; tackifiers.

In the photosensitive composition of the present invention, the content of the blocked isocyanate decane, the polymerizable compound having an ethylenically unsaturated bond, and the optional component other than the photopolymerization initiator (excluding the solvent) may be used depending on the purpose of use. The content of the polymerizable compound having an ethylenically unsaturated bond is preferably 100 parts by mass or less based on 100 parts by mass of the total amount of the polymerizable compound having an ethylenically unsaturated bond.

Further, by using the above polymerizable compound having an ethylenically unsaturated bond together with another organic polymer, the properties of the cured product composed of the photosensitive composition of the present invention can be improved. As the above organic polymerization For example, polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly(meth)acrylic acid, styrene-(meth)acrylic acid copolymer, (methyl) Acrylic-methyl methacrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate Ester polyvinyl butyral, cellulose ester, polypropylene decylamine, saturated polyester, phenol resin, phenoxy resin, polyamidoximine resin, polyamine resin, epoxy resin, etc. Preferred are polystyrene, (meth)acrylic acid-methyl methacrylate copolymer, and epoxy resin.

When the other organic polymer is used, the amount thereof is preferably from 10 to 500 parts by mass based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

In the photosensitive composition of the present invention, a monomer having an unsaturated bond, a chain transfer agent, a sensitizer, a surfactant, melamine or the like can be used in combination.

The monomer having the above unsaturated bond may, for example, be 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate or isodecyl acrylate. , octadecyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, methacrylic acid-2 -Hydroxyethyl ester, 2-hydroxypropyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol Acrylate, second season Pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z condensed water Glycerol ether (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like.

As the chain transfer agent or the sensitizer, a compound containing a sulfur atom is usually used. For example: thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-amidinopropyl)glycine , 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)amine,carbenyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propanoic acid, N-(3 - mercaptopropyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, lauryl (4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto -1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, nonylphenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto a mercapto compound such as 3-pyridylphenol, 2-mercaptobenzothiazole, thioglycolic acid, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate); a disulfide compound obtained by oxidation; an iodoalkyl compound such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid or 3-iodopropanesulfonic acid; trimethylolpropane tris(3- Mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylnonylbenzene Butanediol dithiopropionate, butanediol dithioglycolate, ethylene glycol dithioglycolate, trimethylolpropane trithioglycolate, butanediol dithiopropionic acid Ester, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyl Alkyl trithiopropionate; an aliphatic polyfunctional thiol compound such as the following compound No. C1, tris(2-hydroxyethyl)isocyanurate; and Karenz MT manufactured by Showa Denko BD1, PE1, NR1, and the like.

As the surfactant, a fluorochemical surfactant such as a perfluoroalkyl phosphate or a perfluoroalkyl carboxylate; an anionic system such as a higher fatty acid basic salt, an alkyl sulfonate or an alkyl sulfate; Cationic surfactants such as surfactants, higher amine halides, and quaternary ammonium salts; polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, etc. A nonionic surfactant; an amphoteric surfactant; a surfactant such as a polyoxymethylene surfactant, or these may be used in combination.

Examples of the melamine compound include activities in nitrogen compounds such as (poly)methylol melamine, (poly)hydroxymethyl glycoluril, (poly)hydroxymethylbenzoguanamine, and (poly)hydroxymethylurea. All or a portion (at least 2) of the methylol group (CH ₂ OH group) is a compound etherified with an alkyl group. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and these may be the same or different from each other. Further, the methylol group which is not alkyl etherified can be self-condensed in one molecule or condensed between two molecules, and as a result, an oligomer component can be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril or the like can be used. Among these, melamine which is alkyl etherified, such as hexamethoxymethyl melamine or hexabutoxymethyl melamine, is preferred.

The photosensitive composition of the present invention can be applied to soda glass by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, and dipping. On the supporting substrate of quartz glass, semiconductor substrate, metal, paper, plastic, etc. Further, it may be temporarily applied to a support substrate such as a film, and then transferred to another support substrate, and the application method is not limited.

Further, as the light source of the active light used for curing the photosensitive composition of the present invention, light having a wavelength of 300 to 450 nm can be used, and for example, ultrahigh pressure mercury, mercury vapor arc lamp, carbon arc lamp, xenon arc lamp, or the like can be used. .

Further, by using laser light as an exposure light source, a laser direct drawing method in which an image is directly formed by digital information such as a computer without using a mask can improve productivity and improve resolution or positional accuracy. Suitably, as the laser light, light having a wavelength of 340 to 430 nm is suitably used, and light of a visible light to an infrared light region such as an argon ion laser, a krypton laser, a YAG laser, or a semiconductor laser may be used. By. When such lasers are used, sensitizing dyes capable of absorbing visible light to the infrared light are added.

The photosensitive composition of the present invention (or a cured product thereof) can be used for a photocurable paint or varnish; a photocurable adhesive; a printed circuit board, a color television, a PC screen, a portable information terminal, a digital camera, etc. Color filter in color display liquid crystal display panel; color filter of CCD image sensor; touch panel; electrode material for plasma display panel; powder coating; printing ink; printing plate; adhesive; Composition; photo-forming resin, gel coating; electronic photoresist; plating resist; etching resist; both liquid and dry film; solder resist; insulating film; a color filter, or a resist for forming a structure in a manufacturing step of a plasma display panel, an electroluminescence display device, and an LCD; a package for packaging electrical and electronic parts; a solder resist; a magnetic gas Recording material; micro mechanical parts; waveguide; optical switch; plating mask; etching mask, color test system, fiberglass cable coating, template for screen printing; Material; holographic recording material; image recording material; fine electronic circuit; decolorizing material; detaching material for image recording material; decolorizing material for image recording material using microcapsule, A photoresist material for a brush wiring board; a photoresist material for a UV and visible laser direct image system; a photoresist material or a protective film used for forming a dielectric layer in a successive layer of a printed circuit board, Its use is not particularly limited.

The colored photosensitive composition of the present invention is used for the purpose of forming a black matrix. This black matrix is suitable for a color filter for a display device for an image display device such as a liquid crystal display panel.

Further, the color filter for a display device of the present invention may have optical elements of red, green, blue, orange, purple, and black in addition to the cured product of the present invention.

The above black matrix is preferably formed by the following steps (1) a step of forming a coating film of the coloring photosensitive composition of the present invention (specifically, a coloring alkali-developing photosensitive composition) on a substrate, and (2) using a mask having a specific pattern shape. The step of irradiating the active light with the coating film, (3) the step of developing the film after exposure with a developing solution (specifically, an alkali developing solution), and (4) the step of heating the film after development. Further, the colored photosensitive composition of the present invention is also suitable as a coloring composition which is advantageous as an inkjet method and a transfer method without a developing step.

For the production of a color filter for a liquid crystal display panel or the like, the coloring composition of the present invention or the like can be used, and the steps (1) to (4) described above can be repeated to combine two or more patterns.

[Examples]

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

[Manufacturing Example 1] Synthesis of blocked isocyanate decane No. 1

500 parts by mass of methyl ethyl ketone oxime and 100 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) were placed in a four-necked flask under nitrogen atmosphere to obtain a methyl group. Ethyl ketoxime is dissolved in PGMEA. Next, while maintaining the internal temperature at 40 ° C or lower, stirring was continued, and 200 parts by mass of 3-isocyanate triethoxypropyl decane was added over 1 hour, followed by stirring at an internal temperature of 40 ° C for 1 hour. After confirming that the peak of the isocyanate group had disappeared by IR, blocked isocyanate decane No. 1 was obtained.

[Production Example 2] Synthesis of blocked isocyanate decane No. 2

500 parts by mass of 3,5-dimethylpyrazole and 100 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) were added under a nitrogen atmosphere to make methyl ethyl ketone肟 is dissolved in PGMEA. Then, the internal temperature was maintained at 40 ° C or lower, and stirring was continued. 200 parts by mass of 3-isocyanate triethoxypropyl decane was added over 1 hour, and then the mixture was stirred at an internal temperature of 40 ° C for 1 hour. After confirming that the peak of the isocyanate group had disappeared by IR, blocked isocyanate decane No. 2 as a PGMEA solution was obtained.

[Manufacturing Example 3] Production of alkali-developable photosensitive resin No. 1

3,1 g of 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]decane, 7.52 g of acrylic acid, and 2,6-di-t-butyl-p-cresol 0.080 g, tetrabutylammonium chloride 0.183 g, and PGMEA 11.0 g were stirred at 90 ° C for 1 hour, at 105 ° C for 1 hour, and at 120 ° C for 17 hours. After cooling to room temperature, 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added, and the mixture was stirred at 100 ° C for 5 hours. Further, 12.0 g of 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]decane and 0.080 g of 2,6-di-t-butyl-p-cresol were added. And PGMEA 0.600 g, stirred at 90 ° C for 90 minutes, and stirred at 120 ° C for 5 hours, and then added 24.0 g of PGMEA to obtain an alkali-developable photosensitive resin No. 1 as a PGMEA solution (Mw=4900, Mn=2250, Acid value (solids) 47 mg.KOH/g).

[Manufacturing Example 4] Production of alkali-developable photosensitive resin No. 2

184 g of bisphenolphthalein type epoxy resin (epoxy equivalent 231), 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, and 0.11 g of tetra-n-butylammonium bromide were charged. And PGMEA23g, stirred at 120 ° C for 16 hours. The reaction solution was cooled to room temperature, and 35 g of PGMEA, 59 g of biphenyltetracarboxylic dianhydride, and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ° C for 4 hours, at 100 ° C for 3 hours, at 80 ° C for 4 hours, at 60 ° C for 6 hours, and at 40 ° C for 11 hours. After an hour, PGMEA 90 g was added to obtain an alkali-developable photosensitive resin No. 2 (Mw=5000, Mn=2100, acid value (solid content): 92.7 mgKOH/g) as a PGMEA solution.

[Manufacturing Example 5] Production of alkali-developable photosensitive resin No. 3

Loading 1,1-bis(4'-epoxypropyloxyphenyl)-1-(1"-biphenyl)-1-cyclohexylmethane 43g, acrylic acid 11g, 2,6-di-tert-butyl 0.05 g of p-cresol and 0.11 g of tetrabutylammonium acetate and 23 g of PGMEA were stirred at 120 ° C for 16 hours. After cooling to room temperature, 35 g of PGMEA and 9.4 g of biphenyltetracarboxylic dianhydride were added, and the mixture was stirred at 120 ° C. In addition, 6.0 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ° C for 4 hours, at 100 ° C for 3 hours, at 80 ° C for 4 hours, and at 60 ° C for 6 hours at 40 ° C. After stirring at ° C for 11 hours, 29 g of PGMEA was added to obtain an alkali-developable photosensitive resin No. 3 (Mw=4000, Mn=2100, acid value (solid content) 86 mgKOH/g) of the target PGMEA solution.

[Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-2] Coloring photosensitive composition Production of No. 1 to No. 7, photosensitive composition No. 8 and comparative coloring photosensitive composition No. 1 to No. 2

Coloring photosensitive compositions No. 1 to No. 7 (corresponding to Examples 1-1 to 1-7, respectively) and photosensitive composition No. 8 (corresponding to the following Tables 1 and 2) In the examples 1-8) and the colored photosensitive compositions No. 1 to No. 2 (corresponding to Comparative Example 1-1 and Comparative Example 1-2, respectively). Still, the numbers are for mass.

A-1 blocked isocyanate decane No.1

A-2 blocked isocyanate decane No. 2

A'-1 3-isocyanate propyl triethoxy decane

A'-2 3-glycidoxypropyltriethoxydecane

B-1 Alkali-developed photosensitive resin No.1

B-2 Alkali-developed photosensitive resin No. 2

B-3 Alkali-developed photosensitive resin No.3

B-4 SPC-1000 (acrylic resin; manufactured by Showa Denko)

C-1 IRGACURE907 (photopolymerization initiator; manufactured by BASF Corporation)

C-2 NCI-831 (photopolymerization initiator; manufactured by ADEKA)

C-3 N-1919 (photopolymerization initiator; manufactured by ADEKA)

C-4 NCI-930 (photopolymerization initiator; manufactured by ADEKA)

D-1 KAYARAD R-684 (tricyclodecane dimethanol diacrylate; manufactured by Nippon Kayaku Co., Ltd.)

D-2 ARONIX M-405 (multifunctional acrylate; manufactured by Toagosei Co., Ltd.)

D-3 ARONIX M-402 (multifunctional acrylate; manufactured by Toagosei Co., Ltd.)

E carbon black (MA100; manufactured by Mitsubishi Chemical Corporation)

F-1 cyclohexanone

F-2 PGMEA

[Example 2] Photothermal hardening of a photosensitive composition

1.0 parts by mass of blocked isocyanate decane No. 2, NK ORIGO EA-1020 (bisphenol A epoxy acrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.) 58.8 parts by mass, ARONIX M-313 (polyfunctional acrylate; East Asia) 39.2 parts by mass of a synthetic product company and 1.0 part by mass of NCI-930 were kneaded by a 3-axis roll, followed by stirring and defoaming with a planetary mixer. It was coated on a 50 mm × 25 mm × 4.0 mm thick alkali-free glass using a dispenser to coat a contract size glass. The light of 405 nm was irradiated at 3000 mJ/cm ² by a high-pressure mercury lamp (750 W) passing through a 400 nm short-wavelength filter, and hardened at 120 ° C for 1 hour.

[Comparative Example 2] Comparison of photothermal hardening of photosensitive compositions

The comparative photosensitive composition was cured in the same manner as in Example 2 except that the blocked isocyanate decane No. 2 was not used.

[Evaluation Examples 1-1 to 1-8 and Comparative Evaluation Examples 1-1 to 1-2]

The coloring photosensitive compositions No. 1 to No. 7 obtained in Examples 1-1 to 1-7, the photosensitive composition No. 8 obtained in Example 1-8, and Comparative Examples 1-1 to 1-2 were obtained. The colored photosensitive compositions No. 1 to No. 2 were applied to a glass substrate at 410 rpm × 7 seconds, and dried by a hot plate (90 ° C, 90 seconds). The obtained coating film was exposed to (150 mJ/cm ² ) using an ultrahigh pressure mercury lamp. After developing in a rotary developing machine for 45 seconds using a 2.5% by mass aqueous sodium carbonate solution as a developing solution, the mixture was washed with water, and baked at 230 ° C for 30 minutes to fix the pattern. For the coating film after post-baking, the following evaluation was performed. The results are shown in Tables 1 and 2.

(adhesion test)

According to the checkerboard tape method (lattice method) of JIS K5600-5-6, a cut mark is placed on the film after post-baking, and the obtained test piece is placed in a pressure cooker test machine at 120 ° C / 100% RH / Under 2 conditions, the treatment was carried out for 2 hours. Stripping with tape was performed as an adhesion test by calculating the number of peels in 100 of the checkerboard.

[Evaluation Example 2 and Comparative Evaluation Example 2]

For the test pieces obtained in Example 2 and Comparative Example 2, the joint strength was measured using a universal tester HG-200 (manufactured by Shimadzu Scientific Co., Ltd.). The results are shown in Table 3.

From the above results, it is understood that the colored photosensitive composition of the present invention containing a decane coupling agent composed of blocked isocyanate decane is excellent in adhesion. Therefore, the colored photosensitive composition of the present invention is suitable for a black matrix.

Claims (11)

A photosensitive composition comprising a decane coupling agent comprising blocked isocyanate decane, wherein the blocked isocyanate decane is obtained by reacting an isocyanate compound represented by the following formula (I) with a blocking agent , (wherein R ¹ is represented by an alkyl group having 1 to 8 carbon atoms, n is a number from 1 to 10, a is a number from 1 to 3, b is a number from 0 to 2, and a + b = 3). The photosensitive composition of claim 1, which comprises a polymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator. The photosensitive composition of claim 1, which is alkali developable. The photosensitive composition of claim 1, wherein the blocking agent is an anthracene compound. A colored photosensitive composition characterized by further adding a coloring agent to the photosensitive composition of claim 1. The colored photosensitive composition of claim 5, which comprises a polymerizable compound having an ethylenically unsaturated bond and a photopolymerization initiator. The colored photosensitive composition of claim 5, which contains a black pigment. The colored photosensitive composition of claim 5 which is alkali developable. The colored photosensitive composition of claim 5, wherein the blocking agent is an anthracene compound. A black matrix characterized in that the colored photosensitive composition of claim 5 is hardened on a substrate. A color filter characterized by having a black matrix of claim 10.