KR20170113150A - Method of Forming Colored Cured Product - Google Patents

Abstract

A method of forming a colored cured product in which excessive dissolution due to contact with an organic solvent or an alkaline developer does not easily occur even when baking is performed at a low temperature and the production of a color filter including forming a colored cured product by the above- Method.
A photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a silane coupling agent is used, (D) a silane coupling agent And baking of the colored photosensitive resin composition after exposure is carried out at 80 to 150 ° C.

Description

TECHNICAL FIELD The present invention relates to a method of forming colored cured products,

The present invention relates to a method of forming a colored cured product and a method of producing a color filter including the formation of a colored cured product by a method of forming the colored cured product.

A display body such as a liquid crystal display has a structure in which a liquid crystal layer is sandwiched between two substrates on which pairs of electrodes are formed facing each other. A color filter having pixels of respective colors of red (R), green (G), and blue (B) is formed on the inner side of one substrate. In order to prevent color mixture of different colors in each pixel or to hide the pattern of the electrodes in this color filter, a black matrix arranged in a matrix form is usually formed so as to partition the pixels of R, G, and B colors have.

Generally, a color filter is formed by photolithography. Specifically, first, a black photosensitive composition is coated on a substrate, exposed and developed to form a black matrix. Subsequently, coating, exposure and development are repeated for each of the red (R), green (G) and blue (B) photosensitive compositions to form respective color patterns at predetermined positions to form a color filter.

According to such a method, it is easy to form a pattern of a colored film excellent in dimensional accuracy and positional accuracy. As a method of forming a colored film such as a black matrix by photolithography, a method of forming a colored cured product (colored film) by photolithography using a photosensitive resin composition containing carbon black as a light shielding agent has been proposed See literature 1 and 2).

Japanese Patent Application Laid-Open No. 2000-199967 Japanese Patent Application Laid-Open No. 2011-170075

However, in the formation of a color filter or the like, the application of the photosensitive composition, exposure, and development are repeatedly performed as described above, so that colored cured products such as colored films are often repeatedly exposed to an organic solvent or an alkaline developer. Nevertheless, in a colored cured product formed by a conventionally known method, excessive dissolution occurs by repeated contact with an organic solvent or an alkaline developer.

In this respect, if the colored cured product is baked at a temperature of, for example, about 200 占 폚, the colored cured product may be tightened to suppress excessive dissolution by repeated contact with an organic solvent or an alkaline developer.

However, heating at a high temperature of the colored cured product is not preferable because the color cost may change depending on the point of the energy cost or the kind of the colorant.

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a method of forming a colored cured product which does not cause excessive dissolution due to contact with an organic solvent or an alkaline developer even when baking is performed at a low temperature, And a method of manufacturing a color filter.

The present inventors have found that a colored photosensitive resin composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant and (D) a silane coupling agent is used, (D) And the baking of the colored photosensitive resin composition after exposure is carried out at 80 to 150 캜 to solve the above problems, thereby completing the present invention.

In a first aspect of the present invention,

Forming a coating film by applying the colored photosensitive resin composition on a substrate,

Exposure of the coating film,

A bake at 80 to 160 DEG C of the exposed coated film,

Wherein the colored photosensitive resin composition comprises (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a silane coupling agent,

(D) a silane coupling agent represented by the following formula (D1):

^{_{R D1 d R D2 (3-}} d) Si-R D3 -NH-C (O) -Y D -R D4 -X D ··· (D1)

(D D1), R ^D1 is an alkoxy group, R ^D2 is an alkyl group, d is an integer of 1 to 3, R ^D3 is an alkylene group, and Y ^D is -NH-, -O-, or -S -, R ^D4 is a single bond or an alkylene group, X ^D is a nitrogen heteroaryl group which may have a substituent, may be monocyclic or polycyclic, and the ring which bonds to -Y ^D -R ^D4- in X ^D is nitrogen 6-membered aromatic ring, and -Y ^D -R ^D4 - is bonded to the carbon atom in the nitrogen-containing six-membered aromatic ring.

And a compound represented by the following formula (1).

A second aspect of the present invention is a method for producing a color filter comprising the formation of a colored cured product by the method according to the first aspect.

According to the present invention, even when baking is performed at a low temperature, a method of forming a colored cured product, in which excessive dissolution due to contact with an organic solvent or an alkaline developer does not easily occur, and a method of forming a colored cured product by the above- The color filter can be manufactured in a simple manner.

≪ Method of forming colored cured product &

The method of forming the colored cured product is not particularly limited,

Forming a coating film by applying the colored photosensitive resin composition on a substrate,

Exposure of the coating film,

And baking at 80 to 160 캜 of the exposed coating film.

As the colored photosensitive resin composition, a composition comprising (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a silane coupling agent is used.

The silane coupling agent (D) is represented by the following formula (D1):

^{_{R D1 d R D2 (3-}} d) Si-R D3 -NH-C (O) -Y D -R D4 -X D ··· (D1)

(D D1), R ^D1 is an alkoxy group, R ^D2 is an alkyl group, d is an integer of 1 to 3, R ^D3 is an alkylene group, and Y ^D is -NH-, -O-, or -S -, R ^D4 is a single bond or an alkylene group, X ^D is a nitrogen heteroaryl group which may have a substituent, may be monocyclic or polycyclic, and the ring which bonds to -Y ^D -R ^D4- in X ^D is nitrogen 6-membered aromatic ring, and -Y ^D -R ^D4 - is bonded to the carbon atom in the nitrogen-containing six-membered aromatic ring.

And the like.

The colored photosensitive resin composition contains the silane coupling agent represented by the formula (D1) as the silane coupling agent (D), so that the coating film made of the colored photosensitive composition can be baked at 80 to 160 캜 and contact with the organic solvent or the alkaline developer It is possible to form a colored cured product which is hardly caused by excessive dissolution by the above-mentioned method.

Hereinafter, a specific method of forming the colored photosensitive resin composition and the colored cured film will be described.

≪ Coloring Photosensitive composition >

The colored photosensitive composition (hereinafter also referred to as "coloring composition") comprises (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a silane coupling agent. Hereinafter, a necessary or optional material included in the colored photosensitive composition and a method for preparing the black photosensitive composition will be described.

≪ (A) Photopolymerizable compound >

The coloring composition contains (A) a photopolymerizable compound (hereinafter also referred to as " component (A) "). The component (A) is not particularly limited, and conventionally known photopolymerizable compounds can be used. Among them, a resin having an ethylenic unsaturated group or a monomer having an ethylenic unsaturated group is preferable.

The resin having an ethylenic unsaturated group and the monomer having an ethylenic unsaturated group can be used in combination. When a resin having an ethylenic unsaturated group is combined with a monomer having an ethylenic unsaturated group, the curing property of the black composition is improved and pattern formation is easy.

[Resin Having Ethylenic Unsaturated Group]

Examples of the resin having an ethylenic unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (Meth) acrylate, ethyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, (Meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene glycol di (meth) acrylate, (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Oligomers obtained by polymerizing 1,6-hexanediol di (meth) acrylate, cardo epoxy diacrylate and the like; A polyester (meth) acrylate obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resol type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, (Meth) acrylate resins obtained by reacting an epoxy resin such as a cyydecyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin or a dihydroxybenzene type epoxy resin with (meth) acrylic acid. In addition, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be suitably used. In the present specification, "(meth) acrylic" means "acrylic or methacrylic".

(A) When the photopolymerizable compound is a polymer having an ethylenic unsaturated group, such a polymer is preferably a polymer (A ') having an ethylenic unsaturated group and containing a cardo structure.

As the photopolymerizable compound (A), when a polymer (A ') containing the above-mentioned cardo structure is used, (C) a coloring composition which is easily dispersed well and has excellent storage stability is easily obtained. Further, by using the coloring composition in which the coloring agent (C) is well dispersed, it is easy to produce a color filter exhibiting uniform color.

As the resin having an ethylenic unsaturated group, a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride can be suitably used.

Among them, a compound represented by the following formula (a-1) is preferable. The compound represented by the following formula (a-1) is a compound suitable as the polymer (A ') containing the above-mentioned cardo structure. The compound represented by the formula (a-1) is preferable because of its high photo-curability.

However,

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

[Figure 2]

The formula (a2) of, R ^a1 each independently represents a hydrocarbon group, or a halogen atom, a hydrogen atom, a carbon number of 1 ~ 6, R ^a2 are each independently a hydrogen atom or a methyl group, W is ^a single bond Or a group represented by the following formula (a-3).

[Figure 3]

In the formula (a-1), Y ^a represents a residue other than an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl-undo-methylene tetrahydrophthalic acid, anhydrous chlorodic acid, methyltetrahydrophthalic anhydride, And anhydrous glutaric acid.

In the above formula (a-1), Z ^a represents a residue other than the two acid anhydride groups in the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include anhydrous pyromellitic acid, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

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

The acid value of the resin having an ethylenically unsaturated group is preferably 10 to 150 mgKOH / g, more preferably 70 to 110 mgKOH / g, in the resin solid content. When the acid value is 10 mgKOH / g or more, sufficient solubility in a developer is obtained, which is preferable. When the acid value is 150 mgKOH / g or less, sufficient curability can be obtained and the surface property can be improved, which is preferable.

The mass average molecular weight of the resin having an ethylenic unsaturated group is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. By setting the mass average molecular weight to 1000 or more, good heat resistance and film strength can be obtained, which is preferable. The weight average molecular weight is preferably 40,000 or less, because good developability can be obtained.

[Monomer having an ethylenically unsaturated group]

Monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (Meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic anhydride, itaconic acid, (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl 2-phenoxy-2-hydroxypropyl (meth) acrylate, (Meth) acrylate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate and half (meth) acrylate of phthalic acid derivatives. . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di Acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, diethylene glycol di (meth) acrylate, (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acrylates such as hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate, trimethylhexamethylene diisocyanate, or hexamethylene di Condensation products of polyhydric alcohols with N-methylol (meth) acrylamide, and the like can be used, for example, a reaction product of isocyanate and 2-hydroxyethyl (meth) acrylate), methylene bis (meth) acrylamide, (meth) acrylamide methylene ether Multifunctional Monomers, and triacryl-formal. These multifunctional monomers may be used alone or in combination of two or more.

The content of the component (A) in the coloring composition is preferably from 10 to 70 mass%, more preferably from 20 to 65 mass%, and particularly preferably from 30 to 60 mass%, based on the mass of the solid content of the coloring composition.

<(B) Photopolymerization initiator>

The coloring composition includes (B) a photopolymerization initiator (hereinafter also referred to as &quot; component (B) &quot;). As the photopolymerization initiator (B), various photopolymerization initiators conventionally compounded in the coloring composition can be used as long as the object of the present invention is not impaired.

Specific examples of the photopolymerization initiator (B) include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, O-acetyl -9- ethyl-9H-carbazol-3-yl] ethanone oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl- Dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino- - isoamylbenzoic acid, benzyl- benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone, -Methylthioxanthene, 2-isopropylthioxanthene, 2-ethylthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxybenzoimidazole, Methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone , 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl Benzoin isopropyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, alpha, alpha -methylpyrrolidone, Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1 (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine , 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) 2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) (Trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis -Triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -triazine, 2- (4-methoxyphenyl) ) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) Bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2- - trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4- Styrylphenyl-s-triazine, and the like. These photopolymerization initiators (B) may be used alone or in combination of two or more.

Among such photopolymerization initiators (B), oxime ester-based photopolymerization initiators are preferred.

Among the oxime-based photopolymerization initiators, oxime ester compounds represented by the following formula (B1) are preferable.

[Figure 4]

In the above formula (B1), R ^B1 represents -NO ₂ or -COR ^B5 . R ^B5 represents a heterocyclic group which may have a substituent, a condensed cyclic aromatic group or an aromatic group. R ^B2 to R ^B4 each independently represent a monovalent organic group.

Among the compounds represented by the formula (B1), R ^B1 is -NO ₂ or R ^B5 is a complex having a complex ventilation and condensed cyclic group selected from the aromatic group -COR ^B5 the compound preferably, -NO _2, or R ^B5 is more preferably -COR ^B5 a compound of a heterocyclic group.

As the heterocyclic group represented by R ^B5 , there can be mentioned a heterocyclic group having 5 or more members including at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom, preferably a 5-membered ring or a 6-membered ring. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group, and a pyrazolyl group; A nitrogen-containing 6-membered ring group such as a pyridyl group, a pyranyl group, a pyrimidyl group, or a pyridadinyl group; A nitrogen-containing heterocyclic group such as a thiazolyl group or an isothiazolyl group; A nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group; Thienyl group, and thiopyranyl group; An impurity group such as a furyl group and a pyranyl group; And the like. Among them, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

^Examples of the condensed cyclic aromatic group represented by R ^B5 include a naphthyl group, an anthryl group, and a phenanthryl group. The aromatic group represented by R ^B5 includes a phenyl group.

The heterocyclic group, the condensed cyclic aromatic group, or the aromatic group may have a substituent. Particularly, when R ^B5 is an aromatic group, it is preferable to have a substituent. Examples of such a substituent include -NO ₂ , -CN, -SO ₂ R ^B6 , -COR ^B6 , -NR ^B7 R ^B8 , -R ^B9 , -OR ^B9 , -O-RB ¹⁰ -OR ^B11 and the like.

R ^B6 each independently represents an alkyl group, which may be substituted with a halogen atom, or may be interrupted by an ether bond, a thioether bond, or an ester bond. The alkyl group in R ^B6 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group.

R ^B7 and R ^B8 each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, which may be substituted with a halogen atom, and the alkylene moiety of the alkyl group and the alkoxy group may be substituted by an ether bond, a thioether bond, It may be interrupted. R ^B7 and R ^B8 may combine to form a ring structure. The alkyl group or the alkoxy group in R ^B7 and R ^B8 is preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, And a width period.

The ring structure that R ^B7 and R ^B8 can combine to form is a heterocycle. As the heterocyclic ring, there can be mentioned a heterocyclic ring having at least a nitrogen-containing 5-membered ring, preferably a 5- to 7-membered ring. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include a piperidine ring, a morpholine ring, and a thiomorpholine ring. Among them, a morpholine ring is preferable.

R ^B9 represents an alkyl group in which some or all of the hydrogen atoms may be substituted with a halogen atom. The alkyl group in R ^B9 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^B10 represents an alkylene group. R ^B11 represents an alkyl group, which may be substituted with a halogen atom, or may be interrupted by an ether bond, a thioether bond or an ester bond. Preferable number of carbon atoms and specific examples thereof are the same as those of R ^B6 .

Among them, preferable examples of R ^B5 include a pyrrolyl group, a pyridyl group, a thienyl group, a thiopyraryl group, a benzothienyl group, a naphthyl group, and a phenyl group having a substituent.

In the above formula (B1), R ^B2 represents a monovalent organic group. The organic group is preferably a group represented by -R ^B12 , -OR ^B12 , -COR ^B12 , -SR ^B12 or -NR ^B12 R ^B13 . R ^B12 and R ^B13 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group or a heterocyclic group, The moiety may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R ^B12 and R ^B13 may combine with each other to form a ring structure together with the nitrogen atom.

The alkyl group represented by R ^B12 and R ^B13 preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- N-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, isodecyl and the like A straight chain or branched chain group of The alkyl group may have a substituent. Examples of the substituent group include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

The number of carbon atoms of the alkenyl group represented by R ^B12 and R ^B13 is preferably from 1 to 20, more preferably from 1 to 5. The alkenyl group may be linear or branched. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, an ethenyl group, and a propynyl group. The alkenyl group may have a substituent. Examples of the alkenyl group having a substituent include a 2- (benzoxazol-2-yl) ethenyl group and the like.

The number of carbon atoms of the aryl group represented by R ^B12 and R ^B13 is preferably from 6 to 20, more preferably from 6 to 10. Examples of the aryl group include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl and phenanthryl groups.

The number of carbon atoms of the aralkyl group represented by R ^B12 and R ^B13 is preferably 7 to 20, more preferably 7 to 12. Examples of the aralkyl group include benzyl group,? -Methylbenzyl group,?,? - dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

^Examples of the heterocyclic group represented by R ^B12 and R ^B13 include a heterocyclic group having 5 or more members, preferably 5 to 7 member rings, including at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom. This heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include a pyrrolyl group, a pyridyl group, a pyrimidyl group, a furyl group, and a thienyl group.

In these R ^B12 and R ^B13 , the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.

As the ring structure that R ^B12 and R ^B13 can combine to form, heterocyclic ring may be mentioned. As the heterocyclic ring, there can be mentioned a heterocyclic ring having at least a nitrogen-containing 5-membered ring, preferably a 5- to 7-membered ring. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic ring include a piperidine ring, a morpholine ring, and a thiomorpholine ring.

Among them, R ^B2 is most preferably a methyl group, an ethyl group, a propyl group or a phenyl group.

In the above formula (B1), R ^B3 represents a monovalent organic group. The organic group is preferably an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (B2), or a heterocyclic group optionally having a substituent. Examples of the substituent include the same groups as in the case of R ^B5 . Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

[Figure 5]

In the formula (B2), R ^B14 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, n-pentylene, isopentylene and sec- Chain or branched chain. Among them, R ^B14 is most preferably an isopropylene group.

In the formula (B2), R ^B15 represents a monovalent organic group represented by -NR ^B16 R ^B17 (wherein R ^B16 and R ^B17 each independently represent a monovalent organic group). Among such organic groups, it is preferable that the structure of R ^B15 is represented by the following formula (B3) in that the solubility of the oxime-based photopolymerization initiator can be improved.

[6]

In the formula (B3), R ^B18 and R ^B19 each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of such alkyl groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-pentyl group and the like. Among them, R ^B18 and R ^B19 are most preferably a methyl group.

As the heterocyclic group represented by R ^B3 , a heterocyclic group having 5 or more members, preferably a 5-membered or 6-membered ring containing at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom can be mentioned. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group, and a pyrazolyl group; A nitrogen-containing 6-membered ring group such as a pyridyl group, a pyranyl group, a pyrimidyl group, or a pyridadinyl group; A nitrogen-containing heterocyclic group such as a thiazolyl group or an isothiazolyl group; A nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group; Thienyl group, and thiopyranyl group; An impurity group such as a furyl group and a pyranyl group; And the like. Among them, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

The heterocyclic group may have a substituent. Examples of the substituent include the same groups as in the case of R ^B5 .

In the above formula (B1), R ^B4 represents a monovalent organic group. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of such alkyl groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-pentyl group and the like. Among them, R ^B4 is most preferably a methyl group.

The proportion of the amount of the compound represented by the formula (B1) in the mass of the component (B) is preferably 10 mass% or more, more preferably 30 mass% or more, and particularly preferably 50 mass% or more. The upper limit is not particularly limited, but is, for example, 90 mass% or less, preferably 80 mass% or less.

In particular, (B) indicates the weight, formula (B1) in the component, and R ^B1 is -NO _2, or R ^B5 is a heterocyclic group and condensed cyclic group selected from the aromatic group content of the compound ^B5 upper -COR Is preferably 90 mass% or less, and more preferably 80 mass% or less.

By containing the compound represented by the formula (B1) in such a range in the range of the component (B), it is easy to obtain a colored composition capable of forming a pattern excellent in resolution and excellent in adhesion to a substrate.

The content of the component (B) in the coloring composition is preferably from 1 to 30% by mass, more preferably from 2 to 25% by mass, and particularly preferably from 5 to 20% by mass with respect to the mass of the solid content of the coloring composition.

&Lt; (C) Colorant &gt;

The coloring composition comprises (C) a colorant. The colorant (C) contained in the coloring composition is not particularly limited. For example, a color index (CI) (published by The Society of Dyers and Colourists) is a compound classified as a pigment, It is preferable to use those having the same color index (CI) number.

Examples of suitable yellow pigments include C.I. Pigment Yellow 1 (hereinafter, "CI Pigment Yellow" is the same and only the numbers are described below), 3,11,12,13,14,15,16,17,20,24,31,35,55,60 , 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, , 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, .

Examples of suitable orange pigments include C.I. Pigment Orange 1 (hereinafter, "CI Pigment Orange" is the same and only the numbers are described), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51 , 55, 59, 61, 63, 64, 71, and 73, respectively.

Examples of suitable purple pigments include C.I. Pigment Violet 1 (hereinafter, the same is true of C. I. Pigment Violet), and only numbers are given), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40,

Examples of suitable red pigments include C.I. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 49: 1, 49: 1, 48: 2, 48: 3, 48: 4, 49: 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264 and 265.

Examples of suitable blue pigments include C.I. Pigment Blue 1 (hereinafter, "CI Pigment Blue" is the same and only numbers are listed), 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, .

Examples of pigments of other colors that can be suitably used include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 37, C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Brown pigments such as Pigment Brown 28, C.I. Pigment Black 1, C.I. Pigment Black 7 and the like.

When the colorant (C) is used as a light shielding agent, a black pigment is preferably used as the light shielding agent. Examples of the black pigment include carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, metal sulfides, metal sulfates or metal carbonates, And various pigments. Among these, it is preferable to use carbon black having high light shielding properties.

As the carbon black, known carbon black such as channel black, furnace black, thermal black and lamp black can be used, but it is preferable to use channel black having excellent light shielding properties. Resin-coated carbon black may also be used.

Resin-coated carbon black is low in conductivity compared to carbon black without resin coating, and therefore, when used as a black matrix of a liquid crystal display element such as a liquid crystal display, a low-power-consumption display with low leakage of current and high reliability .

In order to adjust the color tone of the carbon black, the above organic pigment may be suitably added as an auxiliary pigment.

In order to uniformly disperse the above coloring agent in the coloring composition, a dispersing agent may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of a polyethylene imine type, a urethane resin type or an acrylic resin type. Particularly, when carbon black is used as the colorant, it is preferable to use an acrylic resin-based dispersant as the dispersant.

The inorganic pigments and the organic pigments may be used alone or in combination of two or more. When used in combination, the organic pigments are preferably used in an amount of from 10 to 80 parts by mass per 100 parts by mass of the total amount of the inorganic pigments and the organic pigments, And more preferably in the range of 20 to 40 parts by mass.

The amount of the coloring agent (C) to be used in the coloring composition may be appropriately determined depending on the use of the coloring composition, but is preferably from 5 to 70 parts by mass, more preferably from 25 to 70 parts by mass based on 100 parts by mass of the total mass of components other than the solvent in the coloring composition. To 60 parts by mass is more preferable. By setting the thickness within the above range, it is easy to form a black matrix or each coloring layer having a desired pattern shape.

Particularly, in the case of forming a black matrix using a coloring composition, it is preferable to adjust the amount of the light-shielding agent in the coloring composition so that the OD value per 1 μm of the black matrix coating is 4 or more. When the OD value per 1 μm of the coating film in the black matrix is 4 or more, sufficient display contrast can be obtained when the black matrix is used for a black matrix of a liquid crystal display.

It is preferable to add the coloring agent to the coloring composition after preparing a dispersion in which the coloring agent is dispersed at a suitable concentration using a dispersing agent.

&Lt; (D) Silane coupling agent &gt;

(D) The silane coupling agent essentially contains a compound represented by the following formula (D1).

^{_{R D1 d R D2 (3-}} d) Si-R D3 -NH-C (O) -Y D -R D4 -X D ··· (D1)

(D D1), R ^D1 is an alkoxy group, R ^D2 is an alkyl group, d is an integer of 1 to 3, R ^D3 is an alkylene group, and Y ^D is -NH-, -O-, or -S -, R ^D4 is a single bond or an alkylene group, X ^D is a nitrogen heteroaryl group which may have a substituent, may be monocyclic or polycyclic, and the ring which bonds to -Y ^D -R ^D4- in X ^D is nitrogen 6-membered aromatic ring, and -Y ^D -R ^D4 - is bonded to the carbon atom in the nitrogen-containing six-membered aromatic ring.

(D) The silane coupling agent binds or interacts with various components contained in the coloring composition or binds to the surface of a support such as a substrate through an alkoxy group and / or a reactive group bonded to the silicon atom. Therefore, when the silane coupling agent (D) is added to the coloring composition, the exposed portions are easily cured well. When a silane coupling agent containing a silane compound represented by the formula (D1) is used, this effect is remarkable.

Therefore, when a colored composition containing a silane compound represented by the formula (D1) is used as a silane coupling agent, it is easy to form a colored cured product which is hardly dissolved excessively in an organic solvent or an alkaline developer and has good adhesion to a substrate.

In the formula (D1), R ^D1 is an alkoxy group. As to R ^D1 , the number of carbon atoms of the alkoxy group is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2 from the viewpoint of reactivity of the silane coupling agent. Specific preferred examples of R ^D1 include a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec- - hexyloxy group. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable.

The silanol group formed by the hydrolysis of the alkoxy group R ^D1 reacts with the surface or the like of the substrate and thus the adhesion of the coating film formed on the substrate to the surface of the substrate such as a substrate tends to be improved. Therefore, it is preferable that d is 3 in view of improving the adhesion of the coating film to the surface of the support such as the substrate.

In the formula (D1), R ^D2 is an alkyl group. With respect to R ^D2 , the number of carbon atoms of the alkyl group is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 1 or 2 from the viewpoint of reactivity of the silane coupling agent. Specific preferred examples of R ^D2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.

In the formula (D1), R ^D3 is an alkylene group. With respect to R ^D3 , the number of carbon atoms of the alkylene group is preferably from 1 to 12, more preferably from 1 to 6, and particularly preferably from 2 to 4. Specific preferred examples of R ^D3 include a methylene group, a 1,2-ethylene group, a 1,1-ethylene group, a propane-1,3-diyl group, a propane- Butane-1,4-diyl group, butane-1,3-diyl group, butane-1,2-diyl group, butane-1,1-diyl group, butane- Diyl group, pentane-1, 5-diyl group, pentane-1, 5-diyl group, An octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, and a dodecane- have. Of these alkylene groups, a 1,2-ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group are preferable.

Y ^D is -NH-, -O-, or -S-, and is preferably -NH-. Since bonding side shown in, -CO-NH- than the bond represented by -CO-O-, -CO-S- or is hard to receive the hydrolysis, Y ^D is the -NH- containing compound as a silane coupling agent By using the coloring composition, a coating film excellent in adhesion to a support such as a substrate can be formed.

R ^D4 is a single bond or an alkylene group, preferably a single bond. A preferred example of when R ^D4 is an alkylene group is the same as R ^D3 .

X ^D is a nitrogen heteroaryl group which may have a substituent, may be monocyclic or polycyclic, and a ring which is bonded to -Y ^D -R ^D4 - in X ^D is a nitrogen-containing six-membered ring, and -Y ^D -R ^D4 - And is bonded to the carbon atom in the nitrogen-containing six-membered aromatic ring. The reason is unknown. However, when a coloring composition containing such a compound having X ^D as a silane coupling agent is used, a coating film having excellent adhesion to a support such as a substrate can be formed.

When X ^D is a polycyclic heteroaryl group, the heteroaryl group may be a condensed ring of a plurality of monocyclic rings, and a plurality of monocyclic rings may be bonded through a single bond. When X ^D is a polycyclic heteroaryl group, the number of rings contained in the polycyclic heteroaryl group is preferably 1 to 3. When X ^D is a polycyclic heteroaryl group, the ring condensed or bonded to the nitrogen-containing six-member aromatic ring in X ^D may or may not contain a hetero atom, and may not be an aromatic ring or an aromatic ring.

Examples of the substituent which X ^{D which} is a nitrogen-containing heteroaryl group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms A nitro group, a nitro group, an amino group, a hydroxyl group, a mercapto group, a cyano group, a sulfonic acid group, a carboxyl group, and a halogen atom. The number of substituents of X ^D is not particularly limited as long as it does not impair the object of the present invention. The number of substituents of X ^D is preferably 5 or less, more preferably 3 or less. When X ^D has a plurality of substituents, the plurality of substituents may be the same or different.

Preferable examples of X ^D include groups represented by the following formulas.

[Figure 7]

Of the above groups, groups represented by the following formulas are more preferable as X ^D.

[Figure 8]

As specific examples of the compound represented by the formula (D1) described above, the following compounds 1 to 8 can be mentioned.

[Figure 9]

(D) The silane coupling agent may contain a silane coupling agent other than the silane compound represented by the formula (D1). Such a silane coupling agent is not particularly limited.

Suitable examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltri Monoalkyltrialkoxysilanes such as methoxysilane and n-butyltriethoxysilane; Dialkyldialkoxysilanes such as dimethyldimethoxysilane and dimethyldiethoxysilane; Monophenyl trialkoxysilane such as phenyltrimethoxysilane and phenyltriethoxysilane; Diphenyldialkoxysilane such as diphenyldimethoxysilane and diphenyldiethoxysilane; Monovinyl trialkoxysilane such as vinyltrimethoxysilane and vinyltriethoxysilane; (Meth) acryloxy compounds such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropylmethyldiethoxysilane. Alkyl monoalkyl dialkoxysilanes; (Meth) acryloxyalkyltrialkoxysilane such as 3-acryloxypropyltrimethoxysilane; Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Amino group-containing trialkoxysilanes such as methoxysilane; Non-cyclic epoxy group-containing alkyltrialkoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; Non-cyclic epoxy group-containing alkylmonoalkyldialkoxysilanes such as 3-glycidoxypropylmethyldiethoxysilane; Alkyltrialkoxysilanes containing alicyclic epoxy groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane; Alkylmonoalkyl dialkoxysilanes containing an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane; Containing alkyltrialkoxysilanes such as [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane and [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane Silane; Mercaptoalkyltrialkoxysilanes such as 3-mercaptopropyltrimethoxysilane; Mercaptoalkylmonoalkyldialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane; Ureido alkyltrialkoxysilanes such as 3-ureidopropyltriethoxysilane; Isocyanate alkyltrialkoxysilanes such as 3-isocyanatopropyltriethoxysilane; Alkyltrialkoxysilane containing an acid anhydride group such as 3-trimethoxysilylpropylsuccinic anhydride; Imide group-containing alkyltrialkoxysilanes such as Nt-butyl-3- (3-trimethoxysilylpropyl) succinic acid imide; And the like. These silane coupling agents may be used alone or in combination of two or more.

The ratio of the mass of the silane compound represented by the formula (D1) to the mass of the silane coupling agent (D) is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% Most preferably 100% by mass.

The content of the silane coupling agent (D) in the coloring composition is not particularly limited. The content of the silane coupling agent (D) is preferably 1000 to 10,000 ppm by mass, more preferably 1,500 to 9,000 ppm by mass, and particularly preferably 2,000 to 8,000 ppm by mass, with respect to the total mass of the coloring composition.

<(S) Solvent>

The coloring composition preferably contains (S) solvent for dilution. Examples of the solvent (S) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono- (Poly) alkylene glycol moiety such as tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, Ether; (Poly) alkylene ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, Butyl acetate, n-propyl butyrate, isopropyl butyrate, n-butyl butyric acid, methyl pyruvate, ethyl pyruvate, isobutyrate, isobutyrate, isobutyrate, isobutyrate, Other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide.

Of these, alkylene glycol monoalkyl ethers, alkylene glycol monoalkyl ether acetates, ketones, the above-mentioned other ethers, lactic acid alkyl esters and the above-mentioned other esters are preferable, and alkylene glycol monoalkyl ether acetates , Ketones, the above-mentioned other ethers, and the above-mentioned other esters are more preferable. (S) solvents may be used alone or in combination of two or more.

The content of the (S) solvent is preferably such that the solid content of the coloring composition is 1 to 50% by mass, more preferably 5 to 30% by mass.

&Lt; Other components &gt;

The coloring composition may contain, in addition to the components described above, a thermal polymerization inhibitor, a defoaming agent, a surfactant, and the like.

As the thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether and the like can be used. As the antifoaming agent, a silicone-based or fluorine-based compound can be used. As the surfactant, various known heat polymerization inhibitors such as anionic, cationic, and nonionic ones can be used.

&Lt; Preparation method of colored composition &gt;

The coloring composition can be prepared, for example, by mixing a predetermined amount of (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a silane coupling agent and, And is uniformly dispersed and dissolved in the (S) solvent as much as possible.

The coloring composition may be prepared using a master batch in which (C) the coloring agent is dispersed in the (S) solvent in advance in a rich manner.

The obtained coloring composition may be filtered using a filter having a desired opening diameter.

&Lt; Method of forming colored cured product &gt;

Using the coloring composition described above, a colored cured product is formed.

The method of forming the colored cured product is, as described above,

Forming a coating film by applying the colored photosensitive resin composition on a substrate,

Exposure of the coating film,

And baking at 80 to 160 캜 of the exposed coating film.

First, the coloring composition is coated on a substrate using a non-contact type coating device such as a roll coater, a reverse coater, a bar coater, or the like, or a non-contact type coating device such as a spinner (rotary coating device), a curtain flow coater, a die coater or a slit coater to form a coating film do.

After application of the coloring composition, the coating film is usually dried to remove the solvent. The drying method is not particularly limited and includes, for example, (1) a method of drying on a hot plate at 80 DEG C to 120 DEG C, preferably at a temperature of 90 DEG C to 100 DEG C for 60 seconds to 120 seconds, (2) (3) a method of removing the solvent by putting it in a hot air heater or an infrared heater for several tens of minutes to several hours may be used.

Then, an active energy ray such as an ultraviolet ray or an excimer laser beam is irradiated to expose the coating film. The energy dose to be irradiated varies depending on the composition of the coloring composition, but is preferably, for example, about 30 mJ / cm ² to about 2000 mJ / cm ² .

The colored film formed in the black matrix or the black matrix is usually patterned. In the case where the colored cured product is a patterned colored film, the exposure of the coated film is performed in a position-selective manner in accordance with the pattern shape. Although the method of position selective exposure is not limited, position selective exposure is usually performed through a negative type mask.

When the coating film is selectively exposed, the coated film after exposure is patterned in a desired shape by development with an alkaline developer. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the alkali developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium hydroxide.

Then, a front exposed film or a coated film on which exposure and development are performed is provided in the post-baking. Post baking of the exposed coating film is carried out at 80 to 160 캜, preferably at 80 to 150 캜, more preferably at 80 to 100 캜.

The post-baking time is typically 20 to 120 minutes, preferably 20 to 60 minutes, and more preferably 20 to 30 minutes.

Since the post-baking is carried out at such a low temperature, discoloration due to heating is suppressed in the colored cured product formed according to the above method.

When post-baking is performed at the above temperature, it is possible to use a plastic substrate such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) which is used as a substrate of a flexible display.

Since the post bake temperature is lower than the heat resistance temperature of these resins, deformation such as warpage, shrinkage, wrinkles and the like caused by heat in the plastic substrate can be prevented.

The heat-resistant temperature of polyethylene terephthalate (PET) is 120 to 140 ° C, and the heat-resistant temperature of polyethylene naphthalate (PEN) is 150 to 160 ° C.

Further, depending on the type of display, an organic EL element may be mounted on a substrate, and a color filter may be formed on the element. Here, since the heat-resistant temperature of a general organic EL element is about 100 占 폚, the above method can form a color filter without post-baking at 100 占 폚 or less and without damaging the organic EL element.

The colored cured product thus formed is suitably used as a black matrix contained in a color filter, a colored film formed in a black matrix, or the like.

Further, the colored cured product formed in the above-described manner is hardly dissolved excessively even when repeatedly contacted with an organic solvent or an alkaline developer. For this reason, the above-described method of forming a colored cured product is suitable as a method of forming a colored cured product in the production of a color filter in which film formation by a photolithography method using an organic solvent or an alkaline developer is repeatedly performed.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these examples.

[Preparation Example 1]

First, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid 72.0 g, and the mixture was heated and dissolved at 90 to 100 占 폚 while blowing air at a rate of 25 ml / min. Then, the temperature of the solution was gradually elevated while the solution was cloudy, and the solution was completely dissolved by heating at 120 ° C. At this time, the solution gradually became a transparent point group, but stirring was continued. In the meantime, the acid value was measured and the heating and stirring were continued until it was less than 1.0 mg KOH / g. The acid value required 12 hours to reach the target value. The mixture was then cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula (a-4) which was colorless and transparent and solid.

[10]

Then, 600 g of 3-methoxybutyl acetate was added to 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed , The temperature was gradually raised, and the reaction was carried out at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain Resin A-1. The disappearance of the acid anhydride group was confirmed by IR spectrum. This resin A-1 corresponds to the resin represented by the above formula (a-1).

[Examples 1 to 4, Comparative Examples 1 to 5 and Reference Example]

(A) the photopolymerizable compound in the amounts shown in Table 1, the photopolymerization initiator (B), the colorant (C) of the kind described in Table 1, and the coloring agent of the kind described in Table 1 were used in Examples 1 to 4, Comparative Examples 1 to 5, The silane coupling agent shown in Table 1 was dispersed and dissolved in a solvent so that the solid concentration became 20% by mass to obtain a colored photosensitive resin composition. As the solvent, a mixture of 20 mass% of 3-methoxybutyl acetate and 80 mass% of propylene glycol monomethyl ether acetate was used.

As the photopolymerizable compound (A), the following A1 and A2 were used.

A1: Resin A-1 obtained in Preparation Example 1

A2: dipentaerythritol hexaacrylate

(B) a compound having the following structure was used as a photopolymerization initiator.

[Figure 11]

(C) The following C1 and C2 were used as colorants.

C1: Carbon black dispersion "CF Black" (trade name: manufactured by Mikuni Color Company, solids content: 25% by mass)

C2: C.I. &Quot; CF Blue &quot; (trade name: manufactured by Mikuni Color Co., Ltd., solid content: 20 mass%) of Pigment Blue 15:

(D) The following D1 and D2 were used as silane coupling agents.

<D1>

[Figure 12]

<D2>

[Figure 13]

Using the colored photosensitive resin compositions of each of the Examples, Comparative Examples and Reference Examples, the development resistance and the solvent resistance were evaluated according to the following methods. The evaluation results are shown in Table 1.

<Phenomenon resistance>

The colored photosensitive resin composition was coated on a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 60 캜 for 120 seconds to form a coating film having a thickness of 1.0 탆.

Then, the entire surface of the coating film was irradiated with ultraviolet rays at an exposure gap of 50 mu m by using a mirror projection aligner (trade name: TME-150RTO, manufactured by TOPCON CO., LTD.). The exposure dose was 200 mJ / cm ² .

After the exposure, the coated film was dipped in a 0.04 mass% KOH aqueous solution at 26 占 폚 for 50 seconds, and then subjected to post-baking at the post-baking temperature shown in Table 1 for 30 minutes to obtain a substrate for confirmation of the development resistance comprising the colored cured film.

The film thickness of the formed colored cured film was measured using a contact type surface shape measuring instrument (product name: Dektak-3ST, Veeco), and then the same substrate was immersed in 0.04 mass% KOH aqueous solution at 26 캜 for 120 seconds three times , And the film thickness of the colored cured film on the substrate was measured again.

The ratio of the film thickness measured the first time to the film thickness measured the second time (the film thickness after the film was dipped in the alkaline developing solution four times in total) was calculated as the film residual ratio.

A case where the residual film ratio was 95% or more was judged as &quot;? &Quot;, a case where the residual film ratio was less than 95% and 60% or more was judged as &quot; DELTA &quot;, and a case where the residual film rate was less than 60%

<Solvent resistance>

In the same manner as in the evaluation method of the development resistance, a substrate for confirmation of solvent resistance was obtained by forming a coating film, exposing it, immersing it in an alkaline developing solution, and carrying out post-baking to obtain a coloring cured film.

The film thickness of the formed colored cured film was measured using a contact type surface shape measuring instrument (product name: Dektak-3ST, manufactured by Veeco), and then propylene glycol monomethyl ether acetate (PGMEA) was coated on the colored cured film using a spin coater , And then baked at 100 DEG C for 120 seconds. After the PGMEA was removed by pre-baking, the film thickness of the colored cured film on the substrate was measured again.

The ratio of the film thickness measured the second time (the thickness of the film after the application of the PGMEA onto the colored hardened film and the baking) with respect to the film thickness measured at the first time was calculated as the film residual ratio.

A case where the residual film ratio was 95% or more was judged as &quot;? &Quot;, a case where the residual film ratio was less than 95% and 60% or more was judged as &quot; DELTA &quot;, and a case where the residual film rate was less than 60%

From Examples, a coating film comprising a colored photosensitive resin composition containing a silane compound represented by the formula (D1) as a silane coupling agent (D) was subjected to exposure, immersion in an alkaline developer, When baking is performed, it can be seen that the formed colored cured film is difficult to dissolve in an alkaline developer or an organic solvent.

According to Comparative Examples 1 and 2, even when the colored photosensitive resin composition contains the silane compound represented by the formula (D1) as the silane coupling agent (D), when the post-baking temperature is too low, It is difficult to form a hardly colored cured film.

According to the comparative example 3, when the colored photosensitive resin composition does not contain the silane coupling agent (D), it can be seen that only baking at 100 캜 can form only the colored developer hardly soluble in the alkaline developing solution and also in the organic solvent .

According to Comparative Examples 4 and 5, when the colored photosensitive resin composition contains the silane compound having a structure not included in the formula (D1) as the silane coupling agent (D1), even if postbaking is performed at 100 ° C or 150 ° C, It is difficult to form a colored cured film which is difficult to dissolve in both the alkali developing solution and the organic solvent.

Claims (5)

Forming a coating film by applying the colored photosensitive resin composition on a substrate,
The exposure of the coating film,
And baking the exposed coating film at 80 to 160 DEG C,
Wherein the colored photosensitive resin composition comprises (A) a photopolymerizable compound, (B) a photopolymerization initiator, (C) a colorant, and (D) a silane coupling agent,
(D) a silane coupling agent represented by the following formula (D1):
^{_{R D1 d R D2 (3-}} d) Si-R D3 -NH-C (O) -Y D -R D4 -X D ··· (D1)
(D D1), R ^D1 is an alkoxy group, R ^D2 is an alkyl group, d is an integer of 1 to 3, R ^D3 is an alkylene group, and Y ^D is -NH-, -O-, or -S -, R ^D4 is a single bond or an alkylene group, X ^D is a nitrogen heteroaryl group which may have a substituent, may be monocyclic or polycyclic, and the ring which bonds to -Y ^D -R ^D4- in X ^D is nitrogen 6-membered aromatic ring, and -Y ^D -R ^D4 - is bonded to the carbon atom in the nitrogen-containing six-membered aromatic ring.
&Lt; / RTI &gt; The method according to claim 1,
Further comprising developing the exposed coating film,
Wherein the exposure of the coating film is performed in a position-
Wherein the baking is performed on the coated film developed after exposure. The method according to claim 1 or 2,
Wherein the photopolymerizable compound (A) has an ethylenic unsaturated group and contains a polymer (A ') containing a cardo structure. The method according to any one of claims 1 to 3,
Wherein the coloring agent (C) is a light-shielding agent. A method of manufacturing a color filter comprising forming a colored cured product by the method of any one of claims 1 to 4.