JP2000194132A - Color photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color photosensitive resin composition capable of shortening a developing time and giving a suitable tact time in a developing process in manufacturing a color filter by incorporating a photopolymerizable monomer and a photopolymerization initiator and a copolymer having oxyethylene structures on the side chains and a solvent and the like in this resin composition. SOLUTION: The color photosensitive resin composition contains (A) colorants, (B) the (meth)acryl copolymer having carboxyl groups, (C) the photopolymerizable monomer, (D) the photopolymerization initiator, (E) the polymer having the oxyethylene structures on the side chains, and (F) the solvent, and the colorant (A) contains composite metal oxides and the photopolymerization initiator (D) contains a compound derived from s-triazine, and the copolymer (E) has the oxyethylene structures on the side chains mixed with a copolymer having structural units represented by formulae I-III in which (n) is a number of 1-100; R is a 1-20C alkyl or aryl group; and (AO)n is a structure having an oxyethylene skeleton.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition useful for an ultraviolet-curable ink or a photoresist, and more particularly to a colored image (pixel) used for a color liquid crystal display device or an image pickup device. (Also referred to as "photosensitive resin composition").

[0002]

2. Description of the Related Art A color filter in a color liquid crystal display or an image pickup device is usually manufactured by forming three primary color pixels of red, green and blue on a substrate such as glass or a silicon wafer. Further, it is usual to provide a black matrix for shielding light between these pixels. Then, in order to form pixels of these colors, a resist solution containing a pigment corresponding to each color is uniformly applied on a substrate on which a light-shielding layer is formed by a spin coater, and then heated and dried (prebaked). A method of exposing and developing the coating film is adopted, and an image of each color is obtained by repeating these operations for each color required for the color filter. As such a resist, together with a coloring material such as a pigment and a binder resin,
Compositions containing a photopolymerizable monomer and a photopolymerization initiator are often used. In addition, a resist containing a black pigment may be used for forming a black matrix.

As the binder resin used for such a resist, a (meth) acrylic resin excellent in heat resistance, transparency and chemical resistance is used because it affects the properties and quality required for a color filter. ing. Among such (meth) acrylic resins, those which are soluble in an organic solvent and can be developed with an aqueous alkali solution are preferable, and therefore, a linear polymer copolymer having a carboxyl group in a side chain, such as (meth) An acrylic acid / benzyl (meth) acrylate copolymer or the like is used.

[0004]

However, a color filter made from a colored photosensitive resin composition using such a known (meth) acrylic resin has low heat resistance, transparency and chemical resistance. Although excellent, the solubility of the non-exposed part in the alkali developing solution is too low depending on the type of the pigment used in the developing step when manufacturing the color filter. There is a problem in that the time becomes extremely slow, and the takt time in the developing step exceeds the takt time which is a time determined in order not to reduce productivity in each step. In this case, by increasing the acid value of the (meth) acrylic resin, it is possible to increase the dissolution rate of the non-exposed portion in the alkali developer to some extent. However, generally, when the acid value of the (meth) acrylic resin is increased, the solubility in an organic solvent becomes poor, and there is a problem that the polymer is precipitated during the polymerization reaction. On the other hand,
By increasing the temperature of the developing solution in the developing step, the solubility of the non-exposed portion in the developing solution is increased, and the time required for removing the film in the non-exposed portion can be shortened. However, when the temperature of the developing solution is increased, the solubility of the exposed portion in the developing solution is increased, and there is a problem that the surface of the exposed portion is roughened, the film is thinned, and the pattern is chipped.

Accordingly, an object of the present invention is to provide a colored photosensitive resin composition capable of imparting an appropriate tact time by shortening the developing time in a developing step when a color filter is manufactured.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a specific component is contained in a colored photosensitive resin composition containing a coloring material, a binder resin, a photopolymerizable monomer and a photopolymerization initiator. It has been found that excellent results can be obtained by blending as an additive, and the present invention has been completed.

[0007]

That is, the present invention provides a colored photosensitive resin composition containing the following components.

(A) a coloring material, (B) a (meth) acrylic copolymer containing a carboxyl group, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) an oxyethylene skeleton in the side chain. A copolymer, and (F) a solvent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In this specification, "(meth) acryl" is a generic term for acryl and methacryl, and similarly "(meth) acrylate"
In this case, acrylate and methacrylate are collectively referred to, and when "(meth) acrylic acid" is used, acrylic acid and methacrylic acid are collectively referred to. Hereinafter, the present invention will be described in detail.

The colored photosensitive resin composition of the present invention is mainly used as a pigment-dispersed resist, and a coloring material (A), which is usually a pigment, is dispersed in a solvent (F). A carboxyl group-containing (meth) acrylic copolymer (B) called a binder resin, a photopolymerizable monomer (C), a photopolymerization initiator (D), and a copolymer (E) having an oxyalkylene skeleton in a side chain; Optionally, other additives are dissolved or dispersed in the solvent (F).

The coloring material (A) is usually a pigment, and can be an inorganic pigment or an organic pigment usually used for a pigment-dispersed resist. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, iron,
Examples include oxides or composite metal oxides of metals such as cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. When the specific components of the composite metal oxide are shown for each color used in the color filter, as the yellow pigment, TiO ₂ -Sb ₂ O ₃ -NiO or
TiO ₂ -Sb ₂ O ₃ -Cr ₂ O ₃ etc., as brown pigments, ZnO-Fe
₂ O ₃ and ZnO-Fe ₂ O ₃ -Cr ₂ O ₃ are green pigments such as T
iO ₂ -ZnO-CoO-NiO, CoO-Cr ₂ O ₃ -TiO ₂ , CoO-Al ₂ O ₃ -Cr ₂ O ₃
-TiO _{2 and the} like are blue pigments such as CoO-Al ₂ O ₃ -Cr ₂ O ₃
Such as CoO-Al ₂ O ₃ is, as a red pigment, PbCrO ₄ -PbMoO ₄ -
PbSO ₄ etc., and black pigments such as CuO-Cr ₂ O ₃ and
CuO—Fe ₂ O ₃ —Mn ₂ O _{3 and the} like are each mentioned. The crystal structure of these composite metal oxide pigments may be either a rutile type or a spinel type.

Specific examples of the organic pigment include a color index (Color Index) (The Society of Dyers an).
d Colourists), which are classified as Pigment. More specifically, compounds having the following color index (C.I.) numbers are included, but are not limited thereto.

CI Pigment Yellow 20, 24, 31, 53,
83, 86, 93, 94, 109, 110, 117,125, 137, 138, 139,
147, 148, 150, 153, 154, 166 and 173; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43,
51, 55, 59, 61, 6465, and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 14
9, 166, 168, 176,177, 180, 192, 215, 216, 224, 24
2, and 254; CI Pigment Violet 14, 19, 23, 29, 32, 33,
36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6 etc.),
21, 22, 28, 60 and 64; CI Pigment Green 7, 10, 15, 25, 36 and 47; CI Pigment Brown 28; CI Pigment Black 1 and 7, and the like.

These coloring materials (pigments) can be used alone or in combination of two or more.
The copolymer (E) having an oxyethylene skeleton in a side chain, which will be described later in the present invention, is an inorganic pigment, particularly a composite metal oxide, as at least a part of the pigment among the coloring materials (pigments). In a composition using a system pigment, a high effect is exhibited. In this case, of course, an organic pigment may be contained together with the inorganic pigment. The coloring material (A) is preferably from 5 to 80% by weight, more preferably from 10 to 80% by weight, based on the total solid content in the colored photosensitive resin composition.
It is used in the range of 70% by weight.

The carboxyl group-containing (meth) acrylic copolymer (B) serves as a binder to impart alkali developability to the unexposed coating film and to act as a dispersion medium for the coloring material. The carboxyl group-containing (meth) acrylic copolymer is usually obtained by copolymerizing a carboxyl group-containing monomer and one or more unsaturated compounds copolymerizable therewith.

The carboxyl group-containing monomer is an unsaturated carboxylic acid, typically, acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid can be used in combination.

Specific examples of the unsaturated compound copolymerizable with the carboxyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate,
Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate,
Cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) Acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth)
Esters containing cycloaliphatic groups of unsaturated carboxylic acids such as acrylates, pinenyl (meth) acrylates, dicyclopentenyl (meth) acrylates and dicyclopentenyloxyethyl (meth) acrylates; esters such as glycidyl (meth) acrylates Saturated glycidyl carboxylate; monosaturated carboxylate monounsaturated carboxylate of glycols such as oligoethylene glycol monoalkyl ester (meth) acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; These are used for producing the (meth) acrylic copolymer (B),
In addition to the carboxyl group-containing monomer, they may be used alone or in combination of two or more.

Among these monomers copolymerizable with the carboxyl group-containing monomer, (meth) acrylate is preferably used. Of course, in this case, if necessary, an unsaturated compound other than the (meth) acrylic acid ester may be used in combination. Examples of the carboxyl group-containing copolymer preferably used in this field include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate copolymer, methacrylic acid. Acid / methyl methacrylate / styrene copolymer.

In the (meth) acrylic copolymer (B), the unit of the carboxyl group-containing monomer is generally from 10 to 50% by weight, and more preferably from 15 to 50% by weight, based on the whole monomer.
Preferably it is present in the range of 25% by weight. Also,
The (meth) acrylic copolymer (B) preferably has a weight average molecular weight in terms of polystyrene of 10,000 to 400,000, more preferably 20,000 to 300,000. This (meth) acrylic copolymer (B) is generally 5% based on the total solid content in the colored photosensitive resin composition.
The content is in the range of from 90 to 90% by weight, preferably from 10 to 70% by weight.

The photopolymerizable monomer (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator described below, and can be a monofunctional monomer, a difunctional or other polyfunctional monomer. Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Specific examples of the bifunctional monomer include 1,6-
Hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentane Examples thereof include diol di (meth) acrylate, and specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned. Among them, a bifunctional or higher polyfunctional monomer is preferably used. In this case, a monofunctional monomer may be used in combination as needed. Photopolymerizable monomer (C)
Is generally in the range of 0.1 to 60 parts by weight based on a total of 100 parts by weight of the (meth) acrylic copolymer (B) and the photopolymerizable monomer (C) in the colored photosensitive resin composition, Preferably, it is contained in the range of 1 to 30 parts by weight.

The photopolymerization initiator (D) can be any of those commonly used in this field. Examples thereof include acetophenone, benzoin, benzophenone, thioxanthone, s-triazine, and other initiators. Is mentioned. More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.

(A) acetophenone-based initiator diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methylpropane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-
1-one, 2-hydroxy-2-methyl-1- [4-
(1-methylvinyl) phenyl] oligomers of propan-1-one and the like.

(B) Benzoin initiators Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.

(C) Benzophenone initiator Benzophenone, methyl o-benzoylbenzoate,
Phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

(D) Thioxanthone initiator 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone,
4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

(E) s-Triazine initiator (having a trihalomethyl group) 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- (4-methoxynaphthyl)-
1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine,
2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (4-
Diethylamino-2-methylphenyl) ethenyl]-
1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

(F) Other initiators 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl)
-4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone,
2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like.

Among these photopolymerization initiators, in the present invention, s-triazine compounds, particularly s-triazine compounds having a trihalomethyl group, are preferably used. In this case, if necessary, other photopolymerization initiators may be used in combination.

Further, a photopolymerization initiator may be used in combination with a photoinitiator. Specific examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine,
4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene,
9,10-diethoxyanthracene, 2-ethyl-9,
10-diethoxyanthracene and the like. These photoinitiating assistants can be used alone or in combination of two or more.

The photopolymerization initiator (D) comprises a total of 10 (meth) acrylic copolymer (B) and photopolymerizable monomer (C).
The content is generally in the range of 0.1 to 50 parts by weight, preferably in the range of 1 to 40 parts by weight with respect to 0 parts by weight. When a photoinitiator is used in addition to the photoinitiator (D), the total amount of the photoinitiator (D) and the photoinitiator is preferably in the above range.

In the present invention, the coloring material (A), the carboxyl group-containing acrylic copolymer (B),
In addition to the photopolymerizable monomer (C) and the photopolymerization initiator (D), a copolymer (E) having an oxyethylene skeleton in the side chain
Is used. This copolymer (E) is a polymer or an oligomer having at least two types of structural units, and one of them has an oxyethylene unit —CH ₂ CH ₂ in a portion branched from the main chain, that is, in a side chain. It has O-. Specifically, it may be a polyoxyethylene allyl ether compound and a copolymer of another monomer copolymerizable therewith. Specific examples of the polyoxyethylene allyl ether compound include polyoxyethylene monoallyl ether monoalkyl ether, polyoxyethylene monoallyl ether monoaryl ether, polyoxyethylene polyoxypropylene monoallyl ether monoalkyl ether, and polyoxyethylene polyoxyalkylene. Propylene monoallyl ether monoaryl ether and the like. The alkyl in these compounds can usually have about 1 to 20 carbon atoms, and the aryl is usually phenyl or naphthyl, and further, a substituent such as alkyl bonded to these aromatic rings. be able to. The unit derived from the polyoxyethylene allyl ether compound can be typically represented by the following formula (I).

[0032]

In the formula, n represents a number from 1 to 100, and R is
It represents hydrogen, alkyl or aryl having 1 to 20 carbon atoms, typically alkyl or aryl, and (AO) _n represents a structure having an oxyethylene skeleton.

Specific examples of the monomer copolymerizable with the polyoxyethylene monoallyl ether compound include methyl (meth) acrylate, ethyl (meth) acrylate,
Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as butyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl ( Meta)
Acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (Meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, tricyclodecyl (meth) acrylate,
Tricyclodecyloxyethyl (meth) acrylate,
Esters containing alicyclic groups of unsaturated carboxylic acids such as adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; glycols monosaturated carboxylic acid esters such as oligoethylene glycol monoalkyl ester (meth) acrylate monounsaturated carboxylic acid esters; styrene, α-methylstyrene And vinyl aromatic compounds such as vinyltoluene; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile Vinyl compounds; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride; polyoxyalkylene allyl ether compounds other than the polyoxyethylene allyl ether compounds described above, for example, polyoxypropylene Examples include monoallyl ether monoalkyl or aryl ether. These monomers copolymerizable with the polyoxyethylene monoallyl ether compound can be copolymerized with the polyoxyethylene allyl ether compound alone or in combination of two or more.

Preferred examples of the copolymer (E) having an oxyethylene skeleton in the side chain include a polyoxyethylene allyl ether compound, typically a polyoxyethylene monoallyl ether monoalkyl or aryl ether compound. A copolymer obtained by copolymerizing at least maleic anhydride and / or styrene, that is, together with the structural unit of the formula (I), the following formula (II) and / or
There is a copolymer having each structural unit of (III).

[0036]

In particular, at least ternary copolymers having the structural units of the formulas (I), (II) and (III) are advantageous. In this copolymer, the compounds of formulas (I), (II) and (I
Advantageously, each constituent unit of II) usually accounts for at least 1 mol%, more preferably at least 5 mol%. Of course, the copolymer may contain units other than the structural units of the above formulas (I), (II) and (III). N, R and (AO) _{n in} formula (I) are as defined above,
Is generally 2 or more, and specific examples of R include methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, cetyl, myristyl, stearyl, phenyl, naphthyl, methylphenyl, Butylphenyl, nonylphenyl and the like,
(AO) _n includes not only the case where only polyoxyethylene is used, but also the case where polyoxyethylene and polyoxypropylene coexist.

Commercially available copolymers having the structural units of the formulas (I), (II) and (III) include (AO) _n in the formula (I)
Is polyoxyethylene, which can be regarded as a terpolymer of polyoxyethylene monoallyl ether monohydrocarbon ether, maleic anhydride and styrene, "Mariarim AKM-0531" manufactured by NOF Corporation, (AO) _n in the formula (I) is polyoxyethylene and polyoxypropylene, and is a polyoxyethylene monoallyl ether monohydrocarbon ether, polyoxypropylene monoallyl ether monohydrocarbon ether, maleic anhydride and styrene. Nippon Oil & Fats Co., Ltd., which can be regarded as a quaternary copolymer
"Mariarim AFB-1521" is available.

The solvent (F) can be any of those used in this field. As a specific example,
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether Dialkyl ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Alkylene glycol alkyl ether acetates such as methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone Kind;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone Is mentioned. These solvents can be used alone or in combination of two or more. The amount of the solvent (F) used is preferably 50 to 90% by weight, more preferably 60 to 85% by weight, based on the total amount of the colored photosensitive resin composition containing the solvent (F).

The colored photosensitive resin composition of the present invention may contain, if necessary, a filler, another polymer compound, a surfactant (pigment dispersant), an adhesion promoter, an antioxidant, an ultraviolet absorber,
An additive such as an anti-agglomeration material can be mixed and used.
Specific examples of the filler include glass, silica, and alumina, and specific examples of other polymer compounds include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Examples of the (pigment dispersant) include various types such as nonionic, cationic, and anionic types. Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2).
-Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are oxidized. Specific examples of the inhibitor include 2,2'-thiobis (4-methyl-
6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol and the like, specifically, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) as an ultraviolet absorber. ) -5-chlorobenzotriazole, alkoxybenzophenone and the like, and specific examples of the coagulant include sodium polyacrylate and the like.

The colored photosensitive resin composition of the present invention can be prepared, for example, as follows. That is, the coloring material (A) is preliminarily mixed with the solvent (F) and dispersed using a bead mill or the like until the coloring material has an average particle diameter of about 0.2 μm or less. At this time, a dispersant is used if necessary, and the (meth) acrylic copolymer (B)
May be partially or wholly incorporated. In the obtained dispersion (mill base), the remaining (meth) acrylic copolymer (B), the photopolymerizable monomer (C) and the photopolymerization initiator (D), and other components used as necessary Further, if necessary, an additional solvent is added so as to have a predetermined concentration to obtain a desired colored photosensitive resin composition.

The photosensitive resin composition thus prepared is
For example, a black matrix or a colored image can be formed by applying the composition on a substrate, photocuring and developing as described below. First, this composition is spin-coated on a substrate (usually glass), and dried by heating (prebaking) to remove the solvent to obtain a smooth coating film. At this time, the thickness of the coating film is about 1 to 3 μm. The coating film thus obtained is irradiated with ultraviolet rays through a black matrix or a negative mask for forming an image. At this time, it is preferable to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel rays and the mask and the substrate are accurately aligned. Thereafter, the cured coating film is brought into contact with a dilute aqueous alkaline solution to dissolve and develop the non-exposed portions, whereby a desired black matrix or image is obtained. After development, if necessary,
Post-curing (post-baking) for about 0 to 60 minutes can also be performed.

The developer used for the development after the patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide,
Disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate , Potassium borate, ammonia and the like. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine,
Triethylamine, monoisopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferred concentration of the alkaline compound in the alkaline developer is
It is in the range of 0.01 to 10% by weight, more preferably 0.01 to 10% by weight.
03 to 5% by weight.

The surfactant may be any of a nonionic surfactant, a cationic surfactant and an anionic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned. Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzene sulfonate; Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate, and the like. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more. The concentration of the surfactant in the alkali developer is usually 0.1.
It is in the range of 01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.

The above-mentioned application and drying of the photosensitive resin liquid,
Through the operations of patterning exposure to the obtained dried coating film and development, a pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained, and these operations are necessary for the color filter. By repeating the same number of times as the number of colors, a color filter is obtained. That is, the color filter is usually a black matrix and red, green and blue three primary color pixels arranged on the substrate, using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color By performing the above operation, a black matrix or pixel of that color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a desired color also for other colors. As a result, the black matrix and the three primary color pixels can be arranged on the substrate. Of course, the photosensitive resin composition of the present invention can be applied to only one, two, or three of the black matrix and the three primary colors. In addition, since the black matrix which is a light shielding layer may be formed of, for example, a chromium layer,
In this case, of course, it is not necessary to use the colored photosensitive resin composition of the present invention for forming the black matrix.

[0046]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the used amount are based on weight unless otherwise specified.

Synthesis Example 1 The following raw materials were charged into a 500 ml four-necked flask equipped with a stirrer, a cooling tube and a thermometer, and the four-necked flask was immersed in an oil bath under a nitrogen stream, and the internal temperature of the flask was increased to 80%. The reaction was carried out by stirring for 5 hours while maintaining the temperature at ~ 85 ° C.
A propylene glycol monomethyl ether acetate solution of a benzyl methacrylate copolymer resin was obtained. This solution had a solid content concentration of 35%. The polystyrene equivalent weight average molecular weight of this resin was 35,000. This is called resin B1.

Methacrylic acid 23.8 g Benzyl methacrylate 76.2 g (Mole ratio of methacrylic acid / benzyl methacrylate 0.389 / 0.611) Propylene glycol monomethyl ether acetate 185.7 g Azobisisobutyronitrile 2.6 g

Synthesis Example 2 The same operation as in Synthesis Example 1 was carried out except that the charged raw materials were changed as follows, to obtain a propylene glycol monomethyl ether acetate solution of a methacrylic acid / benzyl methacrylate copolymer resin. This solution had a solids concentration of 35
%Met. The polystyrene equivalent weight average molecular weight of this resin was 35,000. This is called resin B2.

Methacrylic acid 20.8 g Benzyl methacrylate 79.2 g (Mole ratio of methacrylic acid / benzyl methacrylate 0.350 / 0.650) Propylene glycol monomethyl ether acetate 185.7 g Azobisisobutyronitrile 2.3 g

The resin B1 and the resin B2 obtained in the above synthesis examples
In addition to the above solutions, the materials used in the examples are as follows, and are indicated by the respective symbols in the tables in the examples. The symbols mainly corresponded to the trade names.

(A) Coloring material SKL-601K: CI Pigment Black 26 (copper, iron,
A manganese-based composite metal oxide) / dispersant / propylene glycol monomethyl ether acetate (solvent) mixed at a weight ratio of 40.7 / 8.2 / 51.1 in a black pigment dispersion mill base [Dainichi Seika Kogyo Co., Ltd. )

(C) Photopolymerizable monomer DPHA: dipentaerythritol hexaacrylate [obtained from Nippon Kayaku Co., Ltd.]

(D) Photopolymerization initiator TAZ-PP: 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine [“Triazine PP” obtained from Nippon Sebel Hegner Co., Ltd.]

(E) Additive AKM-0531: Terpolymer of polyoxyethylene allyl ether hydrocarbon ether, maleic anhydride and styrene [unit in which (AO) _n in formula (I) is an oxyethylene skeleton A copolymer comprising a unit of the formula (II) and a unit of the formula (III), "Mariarim AKM-0 obtained from NOF Corporation
531 ″] AFB-1521: quaternary copolymer of polyoxyethylene allyl ether hydrocarbon ether, polyoxypropylene allyl ether hydrocarbon ether, maleic anhydride and styrene [(AO) _n in the formula (I) is oxyethylene A unit that is a skeleton; a unit that is also an oxypropylene skeleton;
Copolymer comprising units of I) and units of formula (III), "Mariarim AFB-1521" obtained from NOF Corporation] AAB-0851: polyoxypropylene allyl ether hydrocarbon ether, maleic anhydride and styrene Terpolymer (a copolymer having a unit in which (AO) _n in the formula (I) is an oxypropylene skeleton, a unit of the formula (II) and a unit of the formula (III), from Nippon Oil & Fats Co., Ltd. Obtained “Mariarim AAB
-0851 "] RMA-506: Polyoxyethylene alkyl phenyl ether acrylate [obtained from Nippon Emulsifier Co., Ltd.] NL-562: Polyoxyethylene nonyl phenyl ether (HLB (hydrophilic lipophilic balance) = 8.9) [ “Newcol 562” obtained from Nippon Emulsifier Co., Ltd.] NL-568: Polyoxyethylene nonylphenyl ether (HLB = 15.2) [“Newcol 568” obtained from Nippon Emulsifier Co., Ltd.] NL-509: Polyoxyethylene nonyl phenyl ether (HLB = 18.0) [“Newcol 509” obtained from Nippon Emulsifier Co., Ltd.] NL-714: Polyoxyethylene polycyclic aryl ether (HLB = 15.0) [Nippon Emulsifier Co., Ltd. NL-1110: Polyoxyethylene lauryl ether (H
LB = 13.8) [“Newcol 1110” obtained from Nippon Emulsifier Co., Ltd.]

(F) Solvent PGM-Ac: propylene glycol monomethyl ether acetate

Examples 1 to 4 and Comparative Examples 1 to 8 To the millbase "SKL-601K" in the amounts shown in Tables 1 to 3, the other components shown in the same table were added and uniformly mixed. A liquid was obtained. In Tables 1 to 3, the amounts of the mill base and the binder are all values including the amount of the solvent.

A 2-inch square # 7059 glass substrate manufactured by Corning Incorporated was sequentially washed with a neutral detergent, water and alcohol, and then dried. After spin-coating each of the photosensitive resin solutions prepared above on the glass substrate so that the dry film thickness after post-baking becomes 1.3 μm, and then pre-baking at 130 ° C. for 3 minutes in a clean oven, And cooled. The coating film after prebaking was subjected to evaluation of coatability (smoothness) described later.

Next, a line and space mask is placed on the resist-coated substrate after prebaking with a gap of 100 μm, and an ultra-high pressure mercury lamp (365 nm wavelength) manufactured by Ushio Inc. Under atmosphere, 5
Irradiation was performed at an exposure of 00 mJ / cm ² or 200 mJ / cm ² . Thereafter, the coating film is immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at room temperature for a predetermined time to develop the film, washed with water, and post-baked at 230 ° C for 20 minutes. Was done. In the steps up to this point, the minimum developing time, developer solubility, optical density, development residue, pattern residue, and cross-sectional shape described below were evaluated.

On the other hand, instead of the line and space mask, a gray scale mask which is a quartz glass plate whose transmittance is changed stepwise from 1 to 60% is used, and the exposure amount is set at 50%.
A pattern was obtained by performing the same operation as above except that the sensitivity was set to 0 mJ / cm ^2, and the sensitivity was measured by the following method.

<Lithography Characteristic Evaluation Method> Coatability (Smoothness): The coating film after pre-baking was observed with an optical microscope. When the film was a good coating, it was evaluated as x. Minimum development time: The substrate having a resist film after light irradiation was immersed in a developer, and the time required until the non-exposed portion came off the film was defined as the minimum development time. Developer solubility: When the developer after development is observed with the naked eye, no suspended matter is observed, and when the solubility of the unexposed portion in the developer is excellent, a scale-like suspended matter is observed. And the case where the solubility was inferior was evaluated as x. Optical Density (abbreviated as OD value): For the patterned coating film after development and post-baking, use a Macbeth densitometer TR-927 and transmit the optical density using a glass substrate as a reference. Mode. Development residue: The substrate after development was observed with a scanning electron microscope, and the presence or absence of a residue was evaluated in the following three steps. ○ No residue is observed. △ A little residue is observed. × A large amount of residue is observed. Remaining pattern: Exposure was set to 200 mJ / cm ^2, and development was performed by the above-mentioned method for a minimum development time of +10 seconds, and the pattern obtained by observing with a scanning electron microscope whether a 20 μm line portion was chipped was observed. The number (numerator) of the remaining 20 lines of the 20 lines (denominator) having a line width of 20 μm was shown without any pattern. Cross-sectional shape: The cross-section of the pattern is observed with a scanning electron microscope and is vertical (the line width at the top and bottom of the pattern is equal) or forward tapered (the line width at the top of the pattern is smaller than the line width at the bottom of the pattern) ○, and those having an inverse taper (the line width at the upper part of the pattern was larger than the line width at the lower part of the pattern) were ×. Sensitivity: The number of steps of the gray scale mask when the residual film ratio was 100% was converted into an exposure amount.

[0062]

Table 1 Example No. Example 1 Example 2 Example 3 Example 4 ━━━━━━━━━━━━━━━━━━━━━━ Composition (A) Mill base 6.90 parts 7.67 parts 8.18 parts 8.18 parts (B) Binder Resin B1 Resin B2 Resin B2 Resin B2 2.78 parts 3.09 Part 2.84 part 2.84 part (C) DPHA 0.45 part 0.50 part 0.62 part 0.62 part (D) TAZ-PP 0.45 part 0.50 part 0.62 part 0.62 part (E) Additive AKM-0531 AKM-0531 AKM-0531 AFB-1521 0.16 part 0.18 parts 0.19 parts 0.19 parts (F) PGM-Ac 9.26 parts 8.06 parts 7.55 parts 7.55 parts Total 20.00 parts 20.00 parts 20.00 parts 20.00 parts ───────────────────── ────── Performance evaluation results Coatability ○ ○ ○ ○ Minimum development time 60 seconds 90 seconds 70 seconds 60 seconds Developer solubility ○ ○ ○ ○ OD value 3.3 3.3 3.3 3.3 Development residue ○ ○ ○ ○ Pattern remaining 20 / 20 20/20 20/20 20/20 Cross-sectional shape ○ ○ ○ ○ Sensitivity 100mJ / cm ² 100mJ / c m ² 100mJ / cm ² 100mJ / cm ² Overall evaluation ○ ○ ○ ○ ━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0063]

Table 2 Example number Comparative example 1 ^{* 1} Comparative example 2 Comparative example 3 Comparative example 4組成 Composition (A) Mill base 8.18 parts 6.90 parts 6.90 parts 6.90 parts (B) Binder Resin B2 Resin B1 Resin B1 Resin B1 2.84 parts 2.78 parts 2.78 parts 2.78 parts (C) DPHA 0.62 parts 0.45 parts 0.45 parts 0.45 parts (D) TAZ-PP 0.62 parts 0.45 parts 0.45 parts 0.45 parts (E) Additive AAB-0851 RMA-506 NL-562 NL -568 0.19 parts 0.16 parts 0.16 parts 0.16 parts (F) PGM-Ac 7.55 parts 9.26 parts 9.26 parts 9.26 parts Total 20.00 parts 20.00 parts 20.00 parts 20.00 parts ─────────────────性能 Performance evaluation results Coatability × ○ ○ ○ Minimum development time − 50 seconds 80 seconds 60 seconds Developer solubility − × ○ ○ OD value − 3.3 3.3 3.3 Development residue − ○ ○ ○ Pattern remaining − 0/20 0/20 0/20 Cross-sectional shape − No pattern Ha ° turn no sensitivity ^{- 100mJ / cm 2 100mJ / cm} 2 100mJ / cm 2 overall evaluation × × × × ━━━━━━━━━━━━━━━━━━━━━━━━━━━━

^{* 1 In} Comparative Example 1, a uniform coating film could not be obtained due to aggregation of the pigment, so that the lithography characteristics could not be evaluated.

[0065]

[Table 3] Example No. Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 ^{* 2} ━━━━━━━━━━━━━━━━━━━━━━━━━━ Composition (A) Mill base 6.90 parts 6.90 parts 6.90 parts 6.90 parts (B) Binder Resin B1 Resin B1 Resin B1 Resin B1 2.78 parts 2.78 parts 2.78 parts 3.24 parts (C) DPHA 0.45 parts 0.45 parts 0.45 parts 0.45 parts (D) TAZ-PP 0.45 parts 0.45 parts 0.45 parts 0.45 parts (E) Additive NL-509 NL-714 NL-1110 None 0.16 parts 0.16 parts 0.16 parts-(F) PGM-Ac 9.26 parts 9.26 parts 9.26 parts 8.96 parts Total 20.00 parts 20.00 parts 20.00 parts 20.00 parts ──────────────────── ──────── Performance evaluation result Coatability ○ ○ ○ ○ Minimum development time 155 seconds 50 seconds 40 seconds 180 seconds Developer solubility × ○ ○ ○ OD value 3.3 3.3 3.3 3.3 Development residue ○ ○ ○ − Pattern remaining 0/20 0/20 0/20-Sectional shape No pattern No pattern Ha ° without turn - sensitivity ^{100mJ / cm 2 100mJ / cm 2} 100mJ / cm 2 - comprehensive evaluation × × × × ━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━

^{* 2 In} Comparative Example 8, lithography characteristics were not evaluated because the development time was too long, resulting in tact over.

As can be seen from Tables 1 to 3, in Comparative Example 8 in which no additive was used, the development time was too long, resulting in tact over. On the other hand, if a general surfactant is used as in Comparative Examples 2 to 7, the development time can be shortened, but the pattern may be chipped. on the other hand,
AAB-0 having a polyoxyalkylene skeleton in the side chain, but the oxyalkylene skeleton is only oxypropylene
In Comparative Example 1 using 851, no smooth coating film was obtained due to pigment aggregation. On the other hand, in Examples 1 to 4 using the additive having at least an oxyethylene skeleton in the side chain according to the present invention, the development time was shortened, and good results were obtained without chipping of the pattern.

Here, CI Pigment Black 2 which is a copper / iron / manganese composite metal oxide is used as a coloring material.
Although the example using No. 6 was shown, the development time can be shortened without sacrificing other performances similarly when other complex metal oxide pigments are used.

[0069]

When the colored photosensitive resin composition of the present invention is used, the black matrix and the colored pixels obtained by light irradiation and development hardly suffer from chipping of the pattern, and the cross-sectional shape of the pattern does not become reverse tapered. The development time can be reduced while maintaining such performance. Therefore, when a colored filter is produced by using the colored photosensitive resin composition of the present invention as a pigment-dispersed resist, high productivity can be ensured.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09D 133/06 C09D 133/06 4J038 G02B 5/20 101 G02B 5/20 101 G03F 7/004 501 G03F 7/004 501 505 505 7/027 502 7/027 502 7/031 7/031 // C08F 290/06 C08F 290/06 F term (reference) 2H025 AA00 AA03 AB13 AB17 AC01 AD01 BC14 BC32 BC42 CA01 CA28 CB14 CB43 CC03 CC11 CC20 FA03 FA15 2H048 BA45 BA47 BA48 BB42 4J002 BC041 BC042 BE042 BG011 BG041 BG051 BH022 CH052 DE076 DE096 DE106 DE116 DE126 DE136 DE156 EE038 EE058 EH077 EU188 EV308 EW148 FD096 FD147 FD158 Q00 4J011 AA05PA04A13 PA03 PA03 PA38 PA38 PA04 SA31 SA64 SA78 UA01 VA01 WA01 4J027 AC03 AC04 AC06 AC07 AJ02 AJ08 BA02 BA03 BA04 BA05 BA07 BA08 BA09 BA11 BA13 4J038 CC011 CC021 CC022 CC081 CC082 CE052 CF011 CF012 CF021 CF022 CG081 CG132 CH03 CH031 H072 CH081 CH082 CH121 CH172 CH201 CJ131 FA112 GA02 GA06 HA216 KA03 KA06 KA08 MA07 NA18 PA17 PB08 PB09

Claims (4)

[Claims] 1. A colorant, (B) a (meth) acrylic copolymer containing a carboxyl group, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) an oxyethylene skeleton in the side chain. And (F) a solvent. 2. The composition according to claim 1, wherein the coloring material (A) contains a composite metal oxide. 3. The composition according to claim 1, wherein the photopolymerization initiator (D) contains an s-triazine compound. 4. The copolymer (E) having an oxyethylene skeleton in a side chain is represented by the following formulas (I), (II) and (III): (Wherein, n represents a number of 1 to 100, and R represents a carbon number of 1 to 2)
0 represents an alkyl or aryl, and (AO) _n represents a structure having an oxyethylene skeleton).