KR20150027076A - Photosensitive composition - Google Patents

Abstract

상기 착색 감광성 조성물을 기재 상에 있어서 경화하여 이루어지는 블랙 매트릭스이다. 상기한 블랙 매트릭스를 구비하는 컬러 필터이다.A photosensitive composition capable of forming a desired pattern, and a colored photosensitive composition improved in adhesion of a colored pattern to a substrate. Is a photosensitive composition containing a silane coupling agent comprising a block isocyanate silane obtained by reacting an isocyanate compound represented by the following general formula (I) with a blocking agent. (I) A coloring agent is added to the photosensitive composition.

And a black matrix obtained by curing the colored photosensitive composition on a substrate. And is a color filter having the black matrix described above.

Description

[0001] PHOTOSENSITIVE COMPOSITION [0002]

The present invention relates to a photosensitive composition containing a silane coupling agent comprising a block isocyanate silane, a colored photosensitive composition obtained by adding a coloring agent to the photosensitive composition, and a black matrix using the colored photosensitive composition. More specifically, And a black matrix using the same.

The photosensitive resin composition is a photo-curing resin composition, and typical compositions include those containing an ethylenically unsaturated bond-containing compound and a photopolymerization initiator. This photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, and thus is used for photocurable ink, photosensitive printing plate, printed wiring board, various photoresist, and the like.

Particularly, a colored photosensitive resin composition using carbon black as a pigment is useful as a black matrix provided at a boundary portion between coloring layers of R, G and B of a color filter in order to enhance display contrast and coloring effect.

With respect to such a colored photosensitive composition, the adhesion between the black pattern (black matrix) obtained through exposure, development and post-curing and the transparent substrate is insufficient, and while the peeling step for forming the black pattern is repeated, There is a problem that a part of the pattern is peeled at the same time, the pattern is lost, or the exposure hardened part does not remain on the transparent substrate.

Patent Document 1 discloses a photosensitive coloring material for forming a colored pixel pattern containing a compound having both a functional group chemically bonded to a transparent substrate and a functional group possessed by a functional group possessed by the component in the photosensitive coloring material and a silane coupling agent, .

Patent Documents 2 to 4 disclose a silane coupling agent comprising a block isocyanate silane having a specific structure.

Japanese Patent Application Laid-Open No. 2004-191724 Japanese Patent Application Laid-Open No. 08-291186 Japanese Patent Application Laid-Open No. 10-067787 Japanese Patent Application Laid-Open No. 2009-144255

However, the invention described in Patent Document 1 is limited to pattern formation by dry development using a dry film, and there is still room for improvement in adhesion with a substrate. Further, in the cited documents 2 to 4, the use of the silane coupling agent described in each document in the photosensitive resin composition is neither described nor suggested.

Accordingly, an object of the present invention is to provide a photosensitive composition capable of forming a desired pattern, and a colored photosensitive composition improved in adhesion of a colored pattern to a substrate.

As a result of careful examination to solve the above problems, the present inventors have found that a photosensitive composition containing a silane coupling agent composed of a predetermined block isocyanate silane can attain the above object, The inventors of the present invention have found that a colored photosensitive composition to which a colorant is added to the above photosensitive composition is preferable for a black matrix.

That is, the photosensitive composition of the present invention is characterized by containing a silane coupling agent comprising a block isocyanate silane obtained by reacting an isocyanate compound represented by the following general formula (I) with a blocking agent.

(Wherein R ¹ represents an alkyl group having 1 to 8 carbon atoms, n is a number of 1 to 10, a is a number of 1 to 3, b is a number of 0 to 2, and a + b = 3. )

Further, the colored photosensitive composition of the present invention is characterized by adding a colorant to the photosensitive composition.

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

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

Further, the photosensitive composition and the colored photosensitive composition of the present invention are preferably alkali-developable.

Further, in the photosensitive composition and the colored photosensitive composition of the present invention, it is preferable that the blocking agent is an oxime 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 including the black matrix described above.

According to the present invention, it is possible to provide a photosensitive composition capable of forming a desired pattern and further improving the adhesion of a colored pattern to a substrate, and a black matrix using the colored photosensitive composition. The cured product of the colored photosensitive composition of the present invention is preferable for color filters for display devices, liquid crystal display panels, and organic EL display panels.

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

The photosensitive composition of the present invention is characterized by containing a block isocyanate silane obtained by reacting an isocyanate compound represented by the above general formula (I) with a blocking agent. As other components, a polymerizable compound having an ethylenic unsaturated bond, a photopolymerization initiator, and the like are preferable, but not limited thereto.

Further, the colored photosensitive composition of the present invention is obtained by adding a colorant to the photosensitive composition of the present invention. As the colorant, it is preferable to contain a black pigment such as carbon black. By containing a black pigment, it is useful as a photosensitive composition for forming a black matrix. Further, since development can be carried out without burdening the environment, it is preferable to be alkali-developable.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ in the general formula (I) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, iso Heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-pentyl, Octyl, tert-octyl, and the like.

In the above general formula (I), it is preferable that R ¹ is methyl, ethyl or propyl from the viewpoint of ease of obtaining raw materials.

Further, it is preferable that n is 2 to 4 in view of the boiling point. The boiling point is preferably higher than the prebaking temperature and the postbaking temperature.

It is preferable that a is 3 and b is 0 from the viewpoint of adhesion.

As the blocking agent used for obtaining the block isocyanate silane used in the present invention, those conventionally used may be used. For example, carboxylic acid esters such as dimethyl malonate and diethyl malonate; Active methylene compounds such as malonic acid, acetylacetone, and acetoacetic acid esters (such as methyl acetoacetate and ethyl acetoacetate); (MEK oxime), methylisobutylketooxime (MIBK oxime), dimethylketooxime, diethyl < RTI ID = 0.0 > Oxime compounds such as keto oxime; Monohydric alcohols such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, heptanol, hexanol, octanol, isononyl alcohol, stearyl alcohol and benzyl alcohol; Glycol derivatives such as methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and propylene glycol monomethyl ether; Phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol and chlorophenol or isomers thereof: ester containing hydroxyl group such as methyl lactate and amyl lactate; Amine compounds such as dibutylamine, diisopropylamine, di-tert-butylamine, di-2-ethylhexylamine, dicyclohexylamine, benzylamine, diphenylamine, aniline and carbazole; Imine compounds such as ethyleneimine and polyethyleneimine; Alcohol amines such as monomethylethanolamine, diethylethanolamine and triethylethanolamine; lactams such as? -pyrrolidone,? -butyrolactam,? -propiolactam,? -butyrolactam,? -valerolactam and? -caprolactam; Mercaptans such as butyl mercaptan, hexyl mercaptan, and dodecyl mercaptan; Imidazoles such as imidazole and 2-ethylimidazole; Acid amides such as acetanilide, acrylamide, acetic acid amide and dimeric acid amide; Acid imides such as succinic acid imide, maleic acid imide and phthalic acid imide; Urea compounds such as thiourea, ethyleneurea and the like; Benzotriazoles; And pyrazoles such as 3,5-dimethylpyrazole. These may be used singly or two or more of them may be used in combination.

Among the above blocking agents, the dissociation temperature is preferably 100 to 200 ° C in view of being stably present at the time of prebaking and reacting at the time of postbaking, and among them, an oxime compound is preferable.

The blocking reaction for obtaining the block isocyanate silane is carried out by a known reaction method. The addition amount of the blocking agent is usually 1 to 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free (isocyanate) isocyanate groups. The reaction temperature of the blocking reaction is usually 50 to 150 캜, preferably 60 to 120 캜. The reaction time is preferably about 1 to 7 hours. In addition, catalysts and solvents (aromatic hydrocarbon-based, ester-based, ether-based, ketone-based solvents and mixed solvents obtained by mixing two or more thereof) may be added.

In the photosensitive composition of the present invention, the content of the silane coupling agent in the photosensitive composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.5 to 10% by mass in terms of solid content. If the content of the silane coupling agent is less than 0.1% by mass, the adhesion may be insufficient. If the content is more than 30% by mass, the silane coupling agent may precipitate in the photosensitive composition.

In the photosensitive composition of the present invention, a polymerizable compound having an ethylenic unsaturated bond can be used. The polymerizable compound having an ethylenically unsaturated bond is not particularly limited and those conventionally used in a photosensitive composition can be used. Examples of the polymerizable compound include ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride , Unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (Meth) acrylic acid,? -Chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hyromic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, (Meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], and omega -carboxylic polycaprolactone mono Mono (meth) acrylate; (Meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate or a polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as methacrylic acid and methacrylic acid; Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, A1 to No. Butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (Meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylate, aminopropyl acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (Meth) acrylate, 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 Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylol ethane tri (Meth) acrylate oligomers such as trimethylolpropane trimethacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol Esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols; Metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) Acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, and methyl anhydride; (Meth) acrylamide, methylenebis- (meth) acrylamide, diethylenetriamintris (meth) acrylamide, xylenebis (meth) acrylamide, Amides of unsaturated monobasic acids and polyamines such as acrylamide; Unsaturated aldehydes such as acrolein; Unsaturated nitriles such as (meth) acrylonitrile,? -Chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Examples of the organic solvent include styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, Unsaturated aromatic compounds such as vinylbenzyl methyl ether and vinyl benzyl glycidyl ether; Unsaturated ketones such as methyl vinyl ketone; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; Vinyl alcohols such as allyl alcohol and crotyl alcohol; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; Indene such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl Pyridine, a vinyl urethane compound of a hydroxyl group-containing vinyl monomer and a polyisocyanate compound, a vinyl epoxy compound of a hydroxyl group-containing vinyl monomer and a polyepoxy compound.

Compound No. A1

Compound No. A2

Compound No. A3

Compound No. A4

Examples of the polymerizable compound having an ethylenically unsaturated bond include a copolymer of an acrylate ester, a phenol and / or cresol novolac epoxy resin, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, an epoxy acrylate resin, A resin obtained by allowing an unsaturated monobasic acid to react with an epoxy compound such as an epoxy compound represented by the formula (II) and further reacting with a polybasic anhydride may also be used. Among them, a resin obtained by allowing an unsaturated monobasic acid to react with an epoxy compound such as an epoxy compound represented by the following general formula (II) and further reacting with a polybasic acid anhydride is preferable. These compounds preferably contain an unsaturated group in an amount of 0.2 to 1.0 equivalent.

(Wherein X ¹ represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO ₂ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom (s), a halogen atom (s), a halogen atom (s) , 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 alkyl, alkoxy and alkenyl groups may be substituted with a halogen atom , m is an integer of 0 to 10, and an optical isomer present when m is not 0 may be any isomer.

(Wherein Z ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, a phenyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms Y ¹ is an alkyl group having ¹ to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkoxy group having ¹ to 10 carbon atoms. An alkyl group, an alkoxy group and an alkenyl group may be substituted with 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 with a halogen atom, an aryl group having 6 to 20 carbon atoms which may be substituted with 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 with a halogen atom, an arylalkenyl group having 6 to 20 carbon atoms, which may be substituted with a halogen atom, An arylalkyl group of 7 to 20 carbon atoms which may be substituted, a heterocyclic group of 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be an unsaturated bond, -O - or is optionally interrupted by -S-, Z is ^2, and Z ² together may form a contiguous ring, p represents an integer of 0~4, q is an integer from 0 to 8 Shows, r is an integer of 0 to 4, s represents an integer of 0 to 4, the sum of the number of r and s is an integer of 2-4.)

Examples of the unsaturated monobasic acid acting on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate maleate, Acrylate maleate, hydroxypropyl acrylate maleate, dicyclopentadiene maleate, and the like.

Examples of the polybasic acid anhydrides to be reacted after the action of the unsaturated monobasic acid may include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, Acid anhydrides, 2,2'-3,3'-benzophenonetetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol trisanhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid Hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride , Trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenylsuccinic anhydride, methylhydromic anhydride, and the like.

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

That is, the epoxy adduct having a structure in which the carboxyl group of the unsaturated monobasic acid is added in an amount of 0.1 to 1.0 per one epoxy group of the epoxy compound, wherein the amount of the acid of the polybasic acid anhydride It is preferable that the ratio of the anhydride structure is 0.1 to 1.0.

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

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

(Wherein X ¹¹ represents a hydrogen atom or a methyl group, Y ¹¹ represents a divalent linking group, and R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkyl group, an aryl group and an arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the methylene group in the alkyl group and the arylalkyl group may be replaced by -O-, -S-, -CO-, R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a carbon atom and may be interrupted by a bonding group of 0.1? T? 0.65 , 0.3? M? 0.8, 0? N? 0.2, and t + m + n = 1.

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

(Wherein X ¹¹ represents -CR ²⁰ R ²¹ -, -NR ²⁰ -, a bivalent chain hydrocarbon group having 1 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, A divalent aromatic hydrocarbon group having 6 to 35 carbon atoms or a divalent heterocyclic group having 2 to 35 carbon atoms and a group obtained by combining a plurality of these groups, and R ²⁰ and R ^{21 each} represent a hydrogen atom, a carbon atom number An aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms; Z ¹¹ and Z ¹² each independently represent a direct bond, -O-, -S-, ^{_{-SO 2 -, -SO-, -NR 10}} -, -PR 10 - represents the, R ¹⁰ is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms, the number of carbon atoms of 6 to 20 carbon atoms or an aryl group An aryl group and an arylalkyl group may be substituted with a halogen atom, a hydroxyl group or a nitro group, and the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, The tylene group may be interrupted by -O-, -S-, -CO-, -COO-, -OCO- or -NH-, or a bonding group combining these groups, provided that the group represented by the general formula (1) The number of carbon atoms is in the range of 1 to 35).

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

Further, the compound having an acid value may be used after the acid value is adjusted by reacting a monofunctional or multifunctional epoxy compound. By adjusting the acid value of the compound having an acid value, the alkali developability of the photosensitive resin can be improved. The compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond that imparts alkali developability) preferably has an acid value of a solid content of 5 to 120 mgKOH / g, and a monofunctional or multifunctional epoxy compound The amount of use is preferably selected so as to satisfy the 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, isobutyl glycidyl Ether, tert-butylglycidyl ether, pentylglycidyl ether, hexylglycidyl ether, heptylglycidyl ether, octylglycidyl ether, nonylglycidyl ether, decylglycidyl ether, undecylglycidyl Dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, Propylglycidyl ether, p-methoxyethylglycidyl ether, phenylglycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether , 2-methylcyclyl glycidyl ether , 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumyl phenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil , Glycidyl butyrate, vinyl cyclohexane monoxide, 1,2-epoxy-4-vinyl cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, No. A2, No. A3, and the like.

As the polyfunctional epoxy compound, use of at least one compound selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers is preferable because a colored photosensitive resin composition having better characteristics can be obtained.

As the bisphenol-type epoxy compound, an epoxy compound represented by the above-mentioned general formula (II) can be used. In addition, for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.

Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, tri Ethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (Glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) ethane, 1,1,1- Dichloromethyl) methane and the like can be used.

In addition, novolak type epoxy compounds such as phenol novolak type epoxy compounds, biphenyl novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A novolak type epoxy compounds and dicyclopentadiene novolak type epoxy compounds; Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1- Alicyclic epoxy compounds such as epoxyethyl-3,4-epoxycyclohexane; Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and dimeric acid glycityl ester; Glycidyl amines such as tetraglycidyldiaminodiphenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; A dioxide compound such as dicyclopentadiene dioxide; Naphthalene type epoxy compounds; Triphenylmethane type epoxy compounds; Dicyclopentadiene type epoxy compounds and the like can also be used.

Further, the photosensitive composition of the present invention may contain a compound which imparts alkali developability without having an ethylenic unsaturated bond. Such a compound may be a compound which is soluble in an aqueous alkali solution by having an acid value Although not particularly limited, typical examples thereof include alkali soluble novolac resins (hereinafter simply referred to as " novolak resins "). Novolak resins are obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenol include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol , p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, alpha -naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester, 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.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde,? -Phenylpropylaldehyde,? -Phenylpropylaldehyde, o-hydroxybenzaldehyde, m- P-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-hydroxybenzaldehyde, p- Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde and the like are used, and among these compounds, formaldehyde, acetaldehyde and benzaldehyde are preferable. These aldehydes may be used alone or in admixture of two or more. The aldehydes are used in a proportion of preferably 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of the phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as formic acid, oxalic acid and acetic acid. The amount of these acid catalysts to be used is preferably 1 x 10 < ^-4 > to 5 x 10 < ^-1 > In the condensation reaction, water is usually used as the reaction medium. However, when the phenols used in the condensation reaction do not dissolve in the aqueous solution of the aldehyde but become heterogeneous from the beginning of the reaction, a hydrophilic solvent may be used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media to be used is generally 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 suitably adjusted according to the reactivity of the reaction raw material, but is usually from 10 to 200 캜, preferably from 70 to 150 캜. After completion 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 generally raised to 130 to 230 캜, the volatile components are distilled off under reduced pressure, The resin is recovered by flow-casting on a steel belt or the like.

Further, after completion of the condensation reaction, the reaction mixture may be dissolved in the hydrophilic solvent and added with a precipitant such as water, n-hexane or n-heptane to recover the novolak resin, isolate the precipitate, have.

Examples of the compound other than the novolak resin that does not have an ethylenically unsaturated bond and impart an alkali developing property include polyhydroxystyrene or derivatives thereof, styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and the like. .

In the photosensitive composition of the present invention, a photopolymerization initiator can be used. As the photopolymerization initiator, conventionally known compounds can be used. Examples thereof include benzophenone, phenylbiphenylketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethylketal, Propanol, 2-fluoro-2- (4'-methylmercapto) benzoyl propane, thioxanthone, 1-crown- Benzoyl-4-methyldiphenylsulfide, benzoin butyl ether, 2-hydroxy-2-benzoyl propane, 2-hydroxy Benzoyl trichloromethane, 4-phenoxybenzoyl dichloromethane, methyl benzoate, 1,7-bis (9'-acridinyl) heptane, 9- 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, Bis (trichloromethyl) -s-triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl- N-1414, N-1717, N-1919, PZ-408 and NCI are commercially available products. Examples of commercially available products include N-1414, N-1717, N-1919, PZ-408, NCI IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF Corporation), and the like can be given as examples.

In the photosensitive composition of the present invention, the content of the photopolymerization initiator is preferably from 0.1 to 30 mass%, particularly preferably from 0.5 to 10 mass%, in the photosensitive composition of the present invention. If the content of the photopolymerization initiator is less than 0.1% by mass, the curing by exposure may become insufficient, and if it is more than 30% by mass, the initiator may precipitate in the photosensitive composition.

A coloring agent may be added to the photosensitive composition of the present invention to form a colored photosensitive composition. Examples of the colorant include an inorganic colorant and an organic colorant. These coloring materials may be used singly or in combination of two or more kinds.

Examples of the inorganic colorant and organic colorant include a nitroso compound, a nitro compound, an azo compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a phthalocyanine compound, an isoindolinone compound, Indoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acid; Azo dyes, metal complex compounds of cyanine dyes; Lake pigment; A carbon black obtained by a furnace method, a channel method and a thermal method, or a carbon black such as acetylene black, Ketjen black or lamp black; The carbon black is coated with an epoxy resin, the carbon black is dispersed in a solvent in advance in a solvent to adsorb a resin of 20 to 200 mg / g, the carbon black is subjected to acidic or alkaline surface treatment , A DBP oil absorption (oil absorption amount) of not more than 90 ml / 100 g at an average particle diameter of 8 nm or more, a total oxygen amount calculated from CO and CO ₂ in a volatile fraction at 950 占 폚 is 9 per 100 m ² of the surface area of carbon black mg or more; Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon airgel, fullerene; Aniline black, pigment black 7, titanium black; Hydrophobic resin, chromium oxide rust, miloly blue, cobalt rust, cobalt blue, manganese system, ferrocyanide, phosphate salt, interferon, ultramarine, cerulian blue, viridian, emerald green, lead sulfate, yellow lead, zinc sulfur , Iron oxide (red iron oxide (III)), cadmium red, synthetic iron black, umber and the like or organic pigments can be used.

As the inorganic colorant and the organic colorant, commercially available pigments may be used. For example, 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, , 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 colorant and the organic colorant, known dyes can be used. Examples of known dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline Dyes, nitro dyes, indanamine dyes, jade photographic dyes, phthalocyanine dyes, and cyanine dyes.

In the colored photosensitive composition of the present invention, the content of the colorant is preferably 0 to 350 parts by mass, more preferably 0 to 250 parts by mass with respect to 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond . If it exceeds 350 parts by mass, the light transmittance of the cured product and the color filter for a display device using the colored photosensitive composition of the present invention is lowered, and the luminance of the display device is lowered, which is not preferable.

A solvent may further be added to the photosensitive composition and the colored photosensitive composition of the present invention. As the solvent, a solvent capable of dissolving or dispersing the respective components (the block isocyanate silane of the present invention and the like) described above, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl Ketones such as isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; Ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; Ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Alcohol-based solvents such as methanol, ethanol, iso-or n-propanol, iso-or n-butanol and pentyl alcohol; Propylene glycol monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, etc. Ether-based solvent; BTX type solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene-based hydrocarbon oils such as terphenyl oil, D-limonene, and pinene; Paraffin type solvents such as Mineral Spirit, Swazor # 310 (Kosomo Matsuyama Petroleum Co., Ltd.), Sorbessio # 100 (EXXON CHEMICAL CO., LTD.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichlorethylene, methylene chloride, and 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; There may be used a solvent such as tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, tetrahydrofuran, dimethylformamide, These solvents may be used singly or in combination of two or more kinds. Among them, ketones, ether ester solvents and the like, in particular, propylene glycol-1-monomethyl ether-2-acetate and cyclohexanone, when the photosensitive composition contains a polymerizable compound having an ethylenic unsaturated bond, Since the compatibility of the compound having an unsaturated bond with the photopolymerization initiator is good.

In the photosensitive composition of the present invention, the amount of the solvent to be used is preferably such that the concentration (solid content) of the composition other than the solvent is 5 to 30% by mass. If it is less than 5% by mass, it may be difficult to increase the thickness of the film and the desired wavelength light can not be sufficiently absorbed. When the amount exceeds 30% by mass, the preservability of the composition due to precipitation of the photosensitive composition component may be deteriorated, The viscosity may increase and the handling may be lowered.

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, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; The present invention relates to a method for producing a metal oxide fine particle comprising the steps of: forming a layered clay mineral, milky blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, , Platinum, gold, silver and copper. Of these, titanium oxide, silica, 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 based on 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.

By containing an inorganic compound in the photosensitive composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form a sintered product pattern such as a barrier rib pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

These inorganic compounds are preferably used, for example, as fillers, antireflective agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbents,

When a colorant such as a pigment or an inorganic compound is used in the colored photosensitive composition of the present invention, a dispersant may be added. As the dispersing agent, any dispersing agent that can disperse and stabilize the coloring material and the inorganic compound may be used. A commercially available dispersing agent such as BYK series manufactured by Big-Massa, etc. may be used, and a polyester having a basic functional group, , A polymer dispersant composed of polyurethane, a functional group having a nitrogen atom as a basic functional group, a functional group having a nitrogen atom, an amine and / or a quaternary salt thereof, and an amine of 1 to 100 mgKOH / g are preferably used.

The photosensitive composition of the present invention may further contain, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, tert-butyl catechol or phenothiazine; Plasticizers; Adhesion promoters; Fillers; Defoamer; A leveling agent; Surface modifiers; Antioxidants; Ultraviolet absorber; Dispersing aids; An anti-aggregation agent; catalyst; Effect promoters; A crosslinking agent; A common additive such as a thickener can be added.

In the photosensitive composition of the present invention, the content of the block isocyanate silane, the polymerizable compound having an ethylenically unsaturated bond, and an optional component (other than the solvent) other than the photopolymerization initiator is appropriately selected depending on the purpose of use, But it is preferably 50 parts by mass or less based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond.

Further, by using another organic polymer together with the polymerizable compound having an ethylenically unsaturated bond, the properties of the cured product of the photosensitive composition of the present invention can be improved. Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Acrylate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, Amide, saturated polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin. Of these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer and epoxy resin are preferable .

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

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

Examples of the monomer having an unsaturated bond include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, Butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate , Bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, Bisphenol Z diglycidyl ether (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like.

As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. Examples of the acid generator include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercapto But are not limited to, ethane sulfonic acid, 3-mercaptopropane sulfonic acid, 4-mercaptobutane sulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3-pyridinol (2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) A mercapto compound, a disulfide compound obtained by oxidizing the mercapto compound, an iodinated alkylated product such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid or 3-iodopropanesulfonic acid, a trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutylate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bistyropropionate, Trimethylolpropane trisphosphate, trimethylolpropane trisphosphate, trimethylolpropane trisphosphate, trimethylolpropane trisphosphate, trimethylolpropane trisphosphate, trimethylolpropane trisphosphate, tris Pionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tri Thio propionate, the following compound No. Aliphatic polyfunctional thiol compounds such as trimethylolpropane tri (meth) acrylate and tris (2-hydroxyethyl) isocyanurate trimellitate, and car lenses MT BD1, PE1 and NR1 manufactured by Showa Denko KK.

Compound No. C1

Examples of the surfactant include fluorine surfactants such as perfluoroalkylphosphoric acid esters and perfluoroalkylcarboxylic acid salts, anionic surfactants such as higher fatty acid alkali salts, alkylsulfonates and alkylsulfates, higher amine halides, A surfactant such as a nonionic surfactant such as polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride, amphoteric surfactant or silicone surfactant may be used And they may be used in combination.

Examples of the melamine compound include compounds having an active methylol group (CH ₂ OH group) in a nitrogen compound such as (poly) methylol melamine, (poly) methylol glycoluryl, (poly) methylolbenzoguanamine, All or a part (at least two) of them are alkyl-etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group or a butyl group, and they may be the same or different. The methylol group which is not alkyl-etherified may be self-condensed in one molecule or condensed between two molecules, resulting in formation of an oligomer component. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used. Of these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferred.

The photosensitive composition of the present invention can be applied to a substrate such as a soda glass, a quartz glass, a semiconductor substrate, a metal, a paper, a plastic or the like by a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, It can be applied on a support gas. Alternatively, after being applied onto a supporting substrate such as a film, it may be transferred onto another supporting substrate, and the application method thereof is not limited.

As the light source of the active light used for curing the photosensitive composition of the present invention, those which emit light having a wavelength of 300 to 450 nm can be used. For example, ultra high-pressure mercury, mercury vapor arc, carbon arc, Can be used.

Further, by using the laser light for the exposure light source, the laser direct drawing method for forming an image directly from digital information such as a computer without using a mask can improve not only productivity but also resolution and positional accuracy However, it is also possible to use light emitted from a visible region to an infrared region of an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, or the like, though it is preferably used as the laser light with a wavelength of 340 to 430 nm. do. In the case of using these lasers, a sensitizing dye which absorbs the infrared region is applied from the visible region.

The photosensitive composition (or a cured product thereof) of the present invention can be used as a light-curable coating material or varnish, a photo-curable adhesive, a printed substrate, or a color in a color display liquid crystal display panel of a color television, a PC monitor, a portable information terminal, Filter, color filter of CCD image sensor, touch panel, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, dental composition, photo-shaping resin, gel coat, photoresist for electro-engineering, electroplating resist, etching For forming a structure in a process for manufacturing a color filter for a resist, a liquid and a dry film, a solder resist, an insulating film, and various displays for use in a display, or a plasma display panel, an electroluminescence display, A composition for encapsulating resist, electric and electronic parts, a solder resist, a magnetic recording material, A material for producing a three-dimensional object by means of stereolithography, a material for holography recording, an image recording material, a fine image display, and the like can be used as a component, waveguide, optical switch, plating mask, etching mask, color test system, Decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct image systems, sequential printed circuit boards And can be used in various applications such as a photoresist material or a protective film used for forming a dielectric layer in a laminate, and there is no particular limitation on its use.

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

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

The black matrix is obtained by the steps of (1) forming a coating film of the colored photosensitive composition of the present invention (in particular, a colored alkali developing photosensitive composition) on a substrate, (2) (3) a step of developing the film after exposure with a developer (particularly, an alkali developing solution), and (4) a step of heating the film after development. Further, the colored photosensitive composition of the present invention is also useful as an ink jet system without a development process, or as a coloring composition of a transfer system.

The production of a color filter for use in a liquid crystal display panel or the like can be carried out by repeatedly carrying out the steps (1) to (4) above using the coloring composition of the present invention or other coloring compositions and combining patterns of two or more colors.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to these Examples.

[Preparation Example 1] Synthesis of block isocyanate silane No. 1

In a four-necked flask, 500 parts by mass of methyl ethyl ketone oxime and 100 parts by mass of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) were charged in a nitrogen atmosphere to dissolve methyl ethyl ketone oxime in PGMEA. Subsequently, 200 parts by mass of 3-isocyanate triethoxypropylsilane was added over 1 hour while the internal temperature was kept at 40 占 폚 or lower with stirring, and then stirred at an internal temperature of 40 占 폚 for 1 hour. It was confirmed by IR that the peak of the isocyanate group was lost, and a block isocyanate silane No. 1 was obtained.

[Preparation Example 2] Synthesis of block isocyanate silane 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 charged in a nitrogen atmosphere to dissolve methyl ethyl ketone oxime in PGMEA. Subsequently, 200 parts by mass of 3-isocyanate triethoxypropyl silane was added over 1 hour while keeping the inner temperature at 40 占 폚 or lower, and then stirred at an inner temperature of 40 占 폚 for 1 hour. It was confirmed by IR that the peak of the isocyanate group was lost, and a block isocyanate silane No. 2 was obtained as a PGMEA solution.

[Preparation Example 3] Preparation of alkali developable photosensitive resin No. 1

30.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 7.52 g of acrylic acid, 0.080 g of 2,6-di-tert-butyl-p-cresol, 0.183 g of tetrabutylammonium chloride and And 11.0 g of PGMEA was added thereto, followed by stirring at 90 占 폚 for 1 hour, at 105 占 폚 for 1 hour, and at 120 占 폚 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] indane, 0.080 g of 2,6-di-tert-butyl-p-cresol and 0.600 g of PGMEA were added, (Mw = 4900, Mn = 2250, acid value (solid content): 47 mg · KOH) as PGMEA solution, and the mixture was stirred at 120 deg. C for 90 minutes and then added with 24.0 g of PGMEA to obtain an alkali developable photosensitive resin No. 1 / g).

[Preparation Example 4] Preparation of alkali developable photosensitive resin No. 2

184 g of bisphenol fluorene type epoxy resin (epoxy equivalent 231), 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 23 g of PGMEA , And the mixture was stirred at 120 DEG C for 16 hours. The reaction solution was cooled to room temperature, 35 g of PGMEA, 59 g of biphthalic anhydride 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 占 폚 for 4 hours, at 100 占 폚 for 3 hours, at 80 占 폚 for 4 hours, at 60 占 폚 for 6 hours and at 40 占 폚 for 11 hours and then PGMEA , And an alkali developable photosensitive resin No. 2 as a PGMEA solution (Mw = 5000, Mn = 2100, acid value (solid content): 92.7 mgKOH / g).

[Preparation Example 5] Preparation of alkali developable photosensitive resin No. 3

43 g of 1,1-bis (4'-epoxypropyloxyphenyl) -1- (1 "-biphenyl) -1-cyclohexylmethane, 11 g of acrylic acid, 2,6- 0.05 g of cresol, 0.11 g of tetrabutylammonium acetate and 23 g of PGMEA were charged and stirred at 120 DEG C for 16 hours. After cooling to room temperature, 35 g of PGMEA and 9.4 g of biphenyltetracarboxylic anhydride were added, followed by stirring at 120 DEG C for 8 hours. After adding 6.0 g of tetrahydrophthalic anhydride, the mixture was stirred at 120 占 폚 for 4 hours, at 100 占 폚 for 3 hours, at 80 占 폚 for 4 hours, at 60 占 폚 for 6 hours, and at 40 占 폚 for 11 hours. PGMEA (Mw = 4000, Mn = 2100, acid value (solid content): 86 mgKOH / g) as a solution.

[Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-2] Colored photosensitive compositions No. 1 to No. 7, photosensitive composition No. 8, and comparative colored photosensitive compositions No. 1 to No. 2 pharmacy

(Corresponding to each of Examples 1-1 to 1-7), Photosensitive Composition No. 8 (corresponding to Examples 1-8 and 1-7, respectively) were prepared according to the blend of Tables 1 and 2 below. And comparative colored photosensitive compositions No. 1 to No. 2 (corresponding to Comparative Examples 1-1 and 1-2, respectively). The numerical values represent the mass parts.

[Table 1]

[Table 2]

A-1 block isocyanate silane No. 1

A-2 block isocyanate silane No. 2

A'-1 3-isocyanate propyltriethoxysilane

A'-2 3-glycidoxypropyltriethoxysilane

B-1 Alkali developable photosensitive resin No. 1

B-2 Alkali developable photosensitive resin No. 2

B-3 Alkali developable photosensitive resin No. 3

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

C-1 Irgacure 907 (photopolymerization initiator; BASF)

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

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

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

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

D-2 ARONIX M-405 (polyfunctional acrylate, manufactured by Toa Synthetic Chemical Industry Co., Ltd.)

D-3 Aronix M-402 (polyfunctional acrylate, manufactured by Toa Synthetic Chemical Industry Co., Ltd.)

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

F-1 cyclohexanone

F-2 PGMEA

[Example 2] Photo-thermo-setting of photosensitive composition

, 1.0 parts by mass of the block isocyanate silane No. 2, 58.8 parts by mass of NK Oligo EA-1020 (bisphenol A type epoxy acrylate; Shin Nakamura Chemical Co., Ltd.), Aronix M-313 (polyfunctional acrylate; Mass part and 1.0 mass part of NCI-930 were kneaded with 3 rolls, followed by stirring and defoaming with a planetary mixer. Was coated on a non-alkali glass of 50 mm x 25 mm x 4.0 mm thick by a dispenser, and glass of the same size was bonded. Light of 405 nm was irradiated at 3000 mJ / cm ² by a high-pressure mercury lamp (750 W) passed through a 400 nm short-wavelength cut filter, and cured at 120 占 폚 for 1 hour.

[Comparative Example 2] The photothermal curing of the comparative photosensitive composition

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

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

The color photosensitive compositions Nos. 1 to 7 obtained in Examples 1-1 to 1-7, the photosensitive composition No. 8 obtained in Examples 1-8, and the comparative colored photosensitive compositions No.1 to No.2 were coated on a glass substrate under the conditions of 410 rpm x 7 seconds and dried (90 DEG C, 90 seconds) on a hot plate. The obtained coating film was exposed (150 mJ / cm ² ) with an ultra-high pressure mercury lamp. 2.5% by mass aqueous sodium carbonate solution was used as the developing solution, developed with a spin developing machine for 45 seconds, washed well, and post-baked at 230 캜 for 30 minutes to fix the pattern. The coating film after post-baking was evaluated in the following manner. The results are shown in Tables 1 and 2.

(Adhesion test)

A cut mark was formed on the coated film after post baking by a grid tape method (cross-cut method) in accordance with JIS K5600-5-6. The resulting test piece was placed in a pressure cooker tester and heated at 120 ° C / 100% RH / 2 hours. And peeled off with a tape to count the number of peels in 100 grids.

[Evaluation Example 2 and Comparative Evaluation Example 2]

The adhesive strengths of the test pieces obtained in Example 2 and Comparative Example 2 were measured using an universal testing machine HG-200 (manufactured by Shimadzu Scientific Co., Ltd.). The results are shown in Table 3.

[Table 3]

From the above results, the colored photosensitive composition of the present invention containing a silane coupling agent comprising a block isocyanate silane is excellent in adhesion. Thus, the colored photosensitive compositions of the present invention are useful in black matrices.

Claims (11)

A photosensitive composition comprising a silane coupling agent comprising a block isocyanate silane obtained by reacting an isocyanate compound represented by the following general formula (I) with a blocking agent:
[Chemical Formula 1]

(Wherein, in the general formula (1), R represents an alkyl group having 1 to 8 carbon atoms, n is a number of 1 to 10, a is a number of 1 to 3, b is a number of 0 to 2, a + b = 3). The method according to claim 1,
A polymerizable compound having an ethylenically unsaturated bond; And
Containing a photopolymerization initiator
Sensitive composition. The method according to claim 1,
Alkaline developing photosensitive composition. The method according to claim 1,
Wherein the blocking agent is an oxime compound. A colored photosensitive composition comprising a colorant added to the photosensitive composition according to claim 1. 6. The method of claim 5,
A polymerizable compound having an ethylenically unsaturated bond; And
Containing a photopolymerization initiator
Lt; / RTI > 6. The method of claim 5,
A colored photosensitive composition containing a black pigment. 6. The method of claim 5,
An alkaline developing colored photosensitive composition. 6. The method of claim 5,
Wherein the blocking agent is an oxime compound. A black matrix obtained by curing the colored photosensitive composition according to claim 5 on a base material. A color filter comprising the black matrix according to claim 10.