JPH10319583A - Photopolymerizable composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photopolymerizable composition for the color filter and the color filter good in sensitivity and developability and resolution and intimate adhesion. SOLUTION: This photopolymerizable composition for the color filter contains a colorant and a photopolymerization initiator and a polymerizable monomer being a mixture of a (meth)acryl monomer having 3 or 4 (meth)acryl groups in the same one molecule, and a (meth)acryl monomer having >=5 (meth)acryl groups in the same one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable composition for a color filter used in the production of an optical color filter used for a color television, a liquid crystal display device, a solid-state imaging device, a camera, and the like. Regarding the obtained color filter, in detail, it is a photopolymerizable composition for color filters with excellent developability, adhesion, sensitivity, and resolution, and suitable for the production of high light-shielding resin black matrices The present invention relates to a photopolymerizable composition and a color filter using the same.

[0002]

2. Description of the Related Art Generally, a color filter forms a black matrix on the surface of a transparent substrate such as a glass or plastic sheet, and then sequentially forms three or more different hues, such as red, green and blue, in a stripe form. Alternatively, it is formed in a color pattern such as a mosaic shape. The pattern size varies depending on the use of the color filter and each color, but is about 5 to 700 μm. Further, the positional accuracy of the superposition is several μ to several tens μ, and it is manufactured by a fine processing technology with high dimensional accuracy.

[0003] Typical production methods of color filters include a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method.
Among these, in particular, a pigment dispersion method of forming a color filter image by coating a photopolymerizable composition containing a color material on a transparent substrate, repeating image exposure, development, and curing as necessary is a color filter. It is widely used because it has high accuracy such as pixel position and film thickness, has excellent durability such as light resistance and heat resistance, and has few defects such as pinholes.

However, a photopolymerizable composition containing a large amount of a color material is not satisfactory in developability, sensitivity, adhesion and resolution. Particularly, a liquid crystal display is of a high resolution type represented by Hi-Vision or the like. In particular, there is a problem in responding to such problems, and there is a strong demand for improvement in these performances. In addition, color filters have improved contrast, T
To prevent FT malfunction, change black matrix to red, green,
It is common to arrange them in a lattice, stripe or mosaic pattern between blue color patterns.However, from the viewpoint of cost reduction, display quality improvement, environmental issues, etc., the black matrix can also be made by the pigment dispersion method. It has been studied diligently, but it has not been realized yet due to similar problems.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and provides a resist material having sufficient sensitivity, resolution, developability, and adhesion to provide a color filter having high display quality. This enables high-precision and low-cost production. Further, since the resist material of the present invention can also produce a resin black matrix, it is possible to easily produce a color filter having excellent reflectivity and environment.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a (meth) acrylate having three to four (meth) acryl groups as a coloring colorant, a photopolymerization initiator, and a polymerizable monomer.
The inventors have found that the above-mentioned problems can be solved by a photopolymerizable composition using a (meth) acrylic monomer having at least 5 (meth) acrylic groups in the same molecule as the acrylic monomer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises (a) a coloring colorant (b) a photopolymerization initiator (c) as a polymerizable monomer having 3 to 4 (meth) acryl groups in the same molecule as an essential component (meth). A) a mixture of (meth) acrylic monomers having 5 or more (meth) acrylic groups in the same molecule as the acrylic monomer, but usually includes the following binder resins,
It is desirable to incorporate a solvent.

(Binder Resin) A binder resin has a function as a binder for improving compatibility, film forming property, developability and adhesiveness. An organic polymer substance having such an action is mentioned. The organic polymer substance is not particularly limited, but a polymer substance having a carboxyl group is preferred from the viewpoints of developability, adhesion to a substrate, and compatibility with a black coloring material. Such resins are
For example, it can be obtained by copolymerizing a polymerizable monomer having a double bond and a carboxyl group alone or with a polymerizable monomer having other properties.

Further, in the present invention, in order to form a high-sensitivity and high-definition image of a black matrix which is a light-shielding material, and to improve the film strength of the formed matrix, an organic polymer substance is used in which a side-chain ethylenic material is used. Organic polymer substances having an unsaturated double bond are preferred, and copolymers having a side chain ethylenically unsaturated double bond, a carboxy group and a hydroxyl group are more preferably used. Such a copolymer is obtained by, for example, applying the above functional functional group (ethylenically unsaturated double bond) to a polymer such as a styrene copolymer having a carboxyl group or an acrylic copolymer by using various reactions. Obtained by introduction.

Specific examples of the organic polymer substance according to the present invention include styrene monomers such as styrene, α-methyl-styrene and vinyltoluene; acrylic acid, methacrylic acid, cinnamic acid, maleic acid, fumaric acid, and anhydride. Unsaturated group-containing carboxylic acids such as maleic acid and itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth)
Acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, etc., hydroxyphenyl (meth) acrylate, methoxyphenyl (meth)
Esters of (meth) acrylic acid such as acrylate benzyl (meth) acrylate; acrylonitrile; at least one unsaturated compound from vinyl acid such as vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate and vinyl pivalate It can be easily obtained by introducing an ethylenic double bond into a side chain of a copolymer in which a group-containing carboxylic acid is selected as a monomer by a usual polymer reaction or the like.

The polymer reaction for introducing an ethylenically unsaturated double bond into the side chain includes a reaction for forming an organic bond such as an ester bond, an amide bond, an ether bond, an imide bond, and a urethane bond. As an example of the introduction reaction, a part or all of the carboxylic acid group and / or the hydroxyl group of the organic polymer copolymer is converted into glycidyl (meth) acrylate, allyl glycidyl ether, and an alicyclic epoxy group having the following structure. Reaction with an aliphatic epoxy group-containing unsaturated compound such as an unsaturated compound can be mentioned. Since this reaction can be carried out under a mild condition with a high yield, it is desirable because the production is easy and the cost is low.

In particular, an alicyclic epoxy group-containing unsaturated compound is preferable because it can be easily introduced and has excellent physical properties such as film strength, developability, and pigment dispersibility. In this specification, “(meth) acryl” indicates “acryl or methacryl”. The same applies to “(meth) acrylate”.

[0013]

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In the present invention, particularly preferred organic polymer substances include styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, and methoxyphenyl (meth) for the purpose of enhancing the adhesion to the substrate. ) Acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth)
10 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol% of a copolymer monomer having a phenyl group such as acrylsulfonamide,
In addition, a copolymer containing 2 to 50% by weight of (meth) acrylic acid, preferably 5 to 50% by weight, or
A reactant to which 2 to 50 mol%, preferably 5 to 40 mol%, of an epoxy group-containing unsaturated compound is added to all copolymerized monomers is desirable.

The molecular weight of such an organic polymer substance is 1,000 to 1,000, in terms of weight average molecular weight (Mw).
000, preferably 2,000 to 300,000, more preferably 3,000 to 100,000.
If the Mw of the organic polymer substance is significantly lower than this range, film bleeding occurs at the image portion during development, and conversely, if the Mw of the organic polymer material is extremely high, poor removability of the non-image portion occurs during development.

Further, another organic or inorganic polymer may be added for the purpose of improving the performance as a resist and the performance as a color filter. Examples of these organic / inorganic polymers include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyether and copolymer polyether of epichlorohydrin and bisphenol A, polyvinyl alkyl ether, polyamides such as soluble nylon, Polyurethane, polyethylene terephthalate / isophthalate, polyethylene adipate, polytetraethylene adipate, polyester such as polyethylene fumarate, acetylcellulose, polyvinyl formal, polyvinyl butyral, and the like.

(Polymerizable monomer) The present invention relates to a (meth) acrylic monomer having 3 to 4 (meth) acrylic groups in the same molecule as a polymerizable monomer and 5 or more (meth) acrylic groups in the same molecule. There is one feature in that a (meth) acrylic monomer having the following is used in combination. 3 in the same molecule
Specific examples of the (meth) acrylic monomer having from 4 to 4 (meth) acrylic groups (hereinafter abbreviated as 3-4 functional acrylic monomer) include pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, Trimethylol-propaneethylene oxide (hereinafter abbreviated as EO) or propylene oxide (hereinafter abbreviated as P0) modified triacrylate, isocyanuric acid EO or PO modified triacrylate, glycerin PO-added triacrylate, triacryloyloxyethyl phosphate, or methacrylate thereof And the like.

Specific examples of (meth) acrylic monomers having five or more (meth) acrylic groups in the same molecule include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and methacrylates thereof. Urethane acrylate UA-306H, UA-306T, U manufactured by Kyoeisha Chemical Co., Ltd.
A-306I or the like can be used.

Among these (meth) acrylic monomers, pentaerythritol triacrylate or pentaerythritol tetraacrylate is preferred as the tri- or tetra-functional acrylic monomer, and 5- to 6-functional acrylic monomer is preferred as the penta- or more-functional acrylic monomer. Specifically, dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate is preferred. In the present invention, it is particularly preferable to use these preferred acrylic monomers in combination.

3-4 functional (meth) acrylic monomers and 5
As for the compounding ratio of the (meth) acrylic monomer having a higher functionality than that of the (meth) acrylic monomer, when the total of these (meth) acrylic monomers is assumed to be 100%, the 3-4 functional (meth) acrylic monomer is 10-10%.
It is preferred to be in the range of 90% by weight. More preferably, it is in the range of 15 to 85% by weight.

(Photopolymerization Initiator) The photopolymerization initiator of the present invention is a compound that generates radicals by actinic rays and polymerizes a polymerizable monomer. Commonly used compounds can be used as the photopolymerization initiator, for example,
Specifically, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-
(Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6
-Bis (trichloromethyl) -s-triazine, halomethylated triazine derivatives, halomethylated oxadiazole derivatives, 2- (2'-chlorophenyl) -4,5
-Diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl)
Imidazole dimer, 2- (2'-fluorophenyl)
-4,5-diphenylimidazole dimer, 2- (2 '
Biimidazole derivatives such as -methoxyphenyl) -4,5-diphenylimidazole dimer and (4'-methoxyphenyl) -4,5-diphenylimidazole dimer;
Benzoin such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether, benzoin alkyl ethers, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as 1-chloroanthraquinone, Benzanthrone derivative, benzophenone, Michler's ketone, 2
-Methylbenzophenone, 3-methylbenzophenone,
4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p
-Dodecylphenyl) ketone, 2-methyl- (4'-
(Methylthio) phenyl) -2-morpholino-1-propanone, acetophenone derivatives such as 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Thioxanthone, 2,4-
Thioxanthone derivatives such as dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, 9-phenylacridine, 9- ( acridine derivatives such as p-methoxyphenyl) acridine,
Phenazine derivatives such as 9,10-dimethylbenzphenazine, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2 , 3,
4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophenyl
1-yl, di-cyclopentadienyl-Ti-2,6-
Di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophenyl-1-yl,
Di-methylcyclopentadienyl-Ti-bis-2,
3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-
Di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-
And titanocene derivatives such as yl) -phenyl-1-yl.

Among these compounds, biimidazole derivatives, titanocene derivatives, triazine derivatives, and oxadiazole derivatives are preferred because they exhibit excellent performance in sensitivity, resolution, developability, and adhesion. In particular, among these, a complex initiation system combining a biimidazole compound and an aromatic amino compound as a sensitizing dye is particularly preferred. Preferred sensitizing dyes include, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, and 3,3'-
Benzophenone compounds such as diaminobenzophenone and 3,4-diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p
-Dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-
Diethylaminophenyl) 1,3,4-oxazole,
2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5- Bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) ) Quinoline, 2- (p-dimethylaminophenyl) pyrimidine,
Examples thereof include compounds containing a p-dialkylaminophenyl group such as 2- (p-diethylaminophenyl) pyrimidine.

A ternary composite initiator in which an aromatic thiol is further combined with a biimidazole derivative and a sensitizing dye is preferable because resolution and adhesion are further improved. Examples of the aromatic thiol include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoxazole.
Mercaptobenzimidazole, 5-phenyl-2-benzoxazolethiol, 6-methyl-2-benzoxazolethiol, 4-amino-5-methyl-2-pyridinethiol, thiophenol, 2-mercaptobenzyl alcohol, 2-phenoxythio Phenol, 3-
And mercaptophenanthrene. Among these compounds, a thiol compound having a heteroaromatic ring is particularly preferable. Among them, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole have an effect of improving resolution and adhesion. Higher is more preferable.

Particularly, it is preferable to combine a polyfunctional thiol compound in addition to biimidazole and a sensitizing dye in the light-shielding resist for the black matrix, since the adhesion, the curability and the resolution are further improved. Such a polyfunctional thiol compound has two or more mercapto (SH) groups in the same molecule. Particularly, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as a methylene or ethylene group is preferable. Specifically, for example, hexanedithiol, decanedithiol, 1,4-
Dimethyl mercaptobenzene, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate,
Pentaerythritol tetrakisthioglycolate, butanediol bisthiopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, tris trimercaptopropionate (2-hydroxyethyl ) Isocyanurate and the like.

(Coloring material) The coloring material used in the present invention is not particularly limited, and may be selected from dyes, organic pigments and inorganic pigments. It is preferable to use a pigment because of poor heat resistance and the like. For example, barium sulfate, lead sulfate, titanium oxide,
Inorganic pigments such as yellow lead, red iron oxide, chromium oxide, carbon black, etc., anthraquinone pigments, berylen pigments, disazo pigments, phthalocyanine pigments, isoindoline pigments, dioxazine pigments, quinacridone pigments, verinone pigments, triphenylmethane pigments, Organic pigments such as thioindigo pigments and the like can be mentioned. These can be used alone or in combination.

When the coloring material is red, blue or green, organic pigments are preferred in view of dispersion stability and color reproducibility. Particularly, phthalocyanine pigments, dioxazine pigments, anthraquinone pigments, disazo pigments, isoindoline pigments, Indolinone pigments and diketopyrrolopyrrole pigments are preferred.
Examples of the light-shielding pigment include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, and cyanine black. In addition, usable pigments are specifically shown by a color index (CI) number.

C. I. Red; 9, 97, 122, 123,
149, 168, 177, 180, 192, 215, 2
16, 217, 220, 223, 224, 226, 22
7, 228, 240, 254 C.I. I. Blue; 15; 3, 15; 6, 22, 60, 64 C.I. I. Green; 6, 7, 36 C.I. I. Black; 7 C.I. I. Yellow; 20, 24, 86, 93, 109, 11
0, 117, 125, 137, 138, 139, 14
7, 148, 150, 153, 154, 166, 168 C.I. I. Orange; 36, 43, 51, 55, 59, 6
1 C. I. Violet; 19, 23, 29, 30, 3
7, 40, 50 C.I. I. Tea; 23, 25, 26

(Solvent) In the present invention, the solvent is not particularly limited as long as it can dissolve and disperse each of the above-mentioned components. Specifically, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl Caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, balsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apco thinner, butyl ether, diisobutyl ketone , Methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal sol
vent No. 1 and No. 2. Amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 Solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methylbutylketone, methylhexylketone, methylisobutyrate, benzonitrile, ethylpropionate,
Methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate , Propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol Monoethyl A Le acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxy propionate, 3
-Ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol Organic solvents such as acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate Is mentioned.

It is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably 120-1
It has a boiling point of 70 ° C. These solvents are used alone or as a mixture. The content of each component of the photopolymerizable composition for a color filter of the present invention is 0 to 95% by weight, preferably 10 to 10% by weight, based on the solid content excluding the solvent and the coloring material. 80% by weight, more preferably 20 to 70% by weight, the compounding amount of the polymerizable monomer is 10 to 95% by weight, preferably 15 to 80% by weight, more preferably 20 to 70% by weight, and the compounding amount of the photopolymerization initiator. Is preferably 0.1 to 40% by weight, particularly 0.5 to 30% by weight, particularly preferably 0.5 to 20% by weight.

The content of the coloring material is preferably in the range of 20 to 80% by weight, particularly 30 to 70% by weight, based on the total solids in the photopolymerizable composition excluding the solvent. In particular, when carbon black is used as the black pigment, the compounding amount of the carbon black is set to 3.0 to form a black matrix having a high light shielding ratio of 3.5 or more at a film thickness of 1 μm. 30 to 80% by weight, preferably 35 to 75% by weight based on the total solids in the polymerizable composition
% By weight, more preferably in the range of 40 to 70% by weight.

The photopolymerizable composition of the present invention is prepared by using the above-mentioned solvent so as to have a solid content of 5 to 50% by weight, preferably 10 to 30% by weight. desirable. In the present invention, in addition to the components described above, for example, an applicability improver such as an F-based surfactant, a pigment derivative, a surfactant, a pigment dispersant such as a polymer, and polymerization inhibition for stabilizing a photosensitive solution. Components such as agents can be suitably added.

Next, a method for producing the photopolymerizable composition for a color filter of the present invention will be described. In the present invention, the coloring material is a paint conditioner in advance,
Dispersion treatment is performed using a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the coloring material becomes fine particles by the dispersion treatment, the improvement in the transparency of the resist (red, blue, green) or the improvement in the light shielding ability (black) and the improvement in the coating characteristics are achieved.

In the dispersion treatment, the treatment is preferably carried out in a system further using a coloring material and a solvent or a binder resin having a dispersing function, or a dispersant. In particular, it is preferable to use a polymer dispersant since the dispersion stability over time is excellent. In addition, dispersion treatment with a liquid in which all components to be mixed as a resist liquid are mixed is not preferable because highly reactive components may be denatured due to heat generated during dispersion.

When dispersed by a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to several millimeters are preferably used. The dispersing conditions are usually such that the temperature is from 0 ° C. to 100 ° C., preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (colored colorant, solvent, dispersant) and the size of the sand grinder. Next, the colored ink obtained by the dispersion treatment and other components necessary as resist components are added and mixed to form a uniform solution. Since fine dust is often mixed with the photosensitive solution in the manufacturing process, it is desirable to filter the obtained resist photosensitive solution with a filter or the like.

Next, a method for producing a color filter using the photopolymerizable composition for a color filter of the present invention will be described. First, the photopolymerizable composition of the present invention is applied on a transparent substrate by using an application device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, a spray, and the like, and dried. And a light-shielding black matrix image is formed by image exposure, development and, if necessary, heat curing or light curing through the photomask, and this operation is repeated for each of the three colors RGB to form a color filter image.
An image can be formed in the same manner even when the black matrix is formed of chromium, chromium oxide, or the like.

When a pixel of a color filter is formed by using the photopolymerizable composition of the present invention, the pixel has very high sensitivity and high resolution. Therefore, without forming an oxygen barrier layer such as polyvinyl alcohol. An image can be formed by exposure and development. The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited.For example, polyester such as polyethylene terephthalate or polypropylene, polyolefin such as polyethylene, polycarbonate, polymethyl methacrylate, Examples include a thermoplastic plastic sheet of polysulfone, a thermosetting plastic sheet such as an epoxy resin, a polyester resin, and a poly (meth) acrylic resin, and various glass plates. Particularly, a glass plate and a heat-resistant plastic are preferably used from the viewpoint of heat resistance.

Such a transparent substrate is previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as a silane coupling agent and a urethane polymer in order to improve physical properties such as surface adhesiveness. You can also. The coating method is not particularly limited, but the thickness of the resin black matrix after coating and drying is 0.1 to 2 μm, preferably 0.1 to 1.5 μm, more preferably 0.1 to 1 μm.
In a colored pattern such as red, blue, and green, the range is preferably 0.5 to 3 μm, preferably 0.6 to 2.5 μm, and more preferably 0.7 to 2 μm.

For drying, a hot plate, an IR oven, a convection oven, or the like can be used.
Preferred drying conditions are 40 to 150 ° C., and the drying time is 10 seconds to 60 minutes. Light sources used for exposure include, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and the like, and argon ion lasers, YAG lasers, excimer lasers, Examples include a laser light source such as a nitrogen laser.

When only a specific wavelength of irradiation light is used, an optical filter can be used. The development process is not particularly limited as long as it is a solvent capable of dissolving the unexposed resist film. For example, organic solvents such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, many organic solvents have environmental pollution, harm to the human body, and danger of fire. Therefore, it is preferable to use an alkali developing solution having no such danger. Examples of such an alkaline developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, and potassium hydroxide, or diethanolamine, triethanolamine, and tetraalkylammonium hydroxide salts. And an aqueous solution containing an organic alkaline agent.

If necessary, the alkali developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxylic acid group, or the like. Especially,
It is preferable to add a surfactant because many surfactants have an effect of improving developability, resolution, background contamination and the like. For example, as a surfactant for a developer, sodium naphthalene sulfonate group, an anionic surfactant having a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Surfactants and the like. There is no particular limitation on the development processing method,
Usually, it is carried out by a method such as immersion development, spray development, brush development, or ultrasonic development at a development temperature of 10 to 50 ° C, preferably 15 to 45 ° C.

[0041]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Synthesis Example 1 (Synthesis of Dispersant) 32 g of a trimer of tolylene diisocyanate (Mitec GP750A, manufactured by Mitsubishi Chemical Corporation, resin solid content 50 wt%, butyl acetate solution) and dibutyltin dilaurate 0. 02 g was diluted and dissolved with 47 g of PGMEA (propylene glycol monomethyl ether acetate).
Under stirring, one end has a methoxy group and a molecular weight of 1,0.
14.4 g of polyethylene glycol (manufactured by NOF Corporation, UNIOX M-1000) having a molecular weight of 1,00
0 polypropylene glycol (Sanyo Chemical Industry Co., Ltd.)
9.6 g of Sannics PP-1000) and a mixture were added dropwise, and the mixture was further reacted at 70 ° C. for 3 hours. next,
N, N-dimethylamino-1,3-propanediamine 1
g was added and reacted at 40 ° C. for another hour. The amine value of the solution containing the dispersion resin thus obtained was determined by neutralization titration to be 14 mgKOH / g. In addition, the resin content was reduced by a dry-up method (30 minutes at 150 ° C).
The hot plate solvent was removed for one minute and the resin concentration was calculated from the weight change.
t%.

Synthesis Example 2 (Synthesis of Binder Resin) 20 g of a styrene / acrylic acid resin having an acid value of 200 and a weight average molecular weight of 5,000, 0.2 of p-methoxyphenol
g, dodecyltrimethylammonium chloride 0.2
g, 40 g of PGMEA were charged into a flask, and (3,4-
7.6 g of epoxycyclohexyl) methyl acrylate
Was added dropwise and reacted at a temperature of 100 ° C. for 30 hours. The reaction solution was reprecipitated in water and dried to obtain a resin. When the neutralization titration with KOH was performed, the acid value of the resin was 80.

Production of Colored Ink Red ink C.I. I. 20 g of Red177 and 10 g of the dispersant of Synthesis Example-1 as a solid content were added, and PGMEA was added.
And adjusted to have a solid content of 30 wt%. This was premixed with a stirrer and dispersed for 8 hours with a paint shaker. For dispersion, zirconia beads having a diameter of 0.5 mm and beads having the same weight as the dispersion ink were added and dispersed. Dispersion was carried out such that the ink temperature was in the range of 25 to 50 ° C. After the dispersion was completed, the ink and beads were separated by a filter.

2. Blue ink The red pigment is C.I. I. Dispersion was carried out in the same manner as for the red ink except that Blue 15; 3 was used. 3. Green ink The red pigment is the green pigment C.I. I. Green 3
The dispersion was carried out in the same manner as for the red ink, except that the dispersion was changed to 6. 4. Black ink 20 g of carbon black MA-220 (manufactured by Mitsubishi Chemical Corporation) as a black pigment, and 2 parts of the dispersant of Synthesis Example 1 as a solid component
g, and dispersed in the same manner as for the red ink except that the solid content was reduced to 50 wt% by dilution with PGMEA.

Examples 1 to 9 and Comparative Examples 1 to 6 1) Preparation of resist solution Using the above-described colored ink, each component was added so that the solid content was as shown below, and the mixture was stirred and dissolved by a stirrer to expose a resist. A liquid was obtained. This photosensitive solution was filtered with a membrane filter before coating.

Red, blue, green resist binder resin (Synthesis Example-2) 30 g Polymerizable monomer (described in Table 1) 20 g Initiator 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer 2g 4,4-'bis (diethylaminobenzophenone) 1
g 2-mercaptobenzothiazole 2 g ・ Pigment (red, blue or green) 30 g ・ Dispersant (Synthesis Example-1) 15 g ・ Solvent (PGMEA) 300 g

Black resist binder resin (Synthesis Example-2) 25 g Polymerizable monomer (described in Table 1) 15 g Initiator 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer 2 g 4,4 -'Bis (diethylaminobenzophenone)
1 g pentaerythritol tetrakisthiopropionate
2g ・ Pigment (carbon black) 50g ・ Dispersant (Synthesis Example-1) 5g ・ Solvent (PGMEA) 300g

2) Evaluation of resist A resist photosensitive liquid was applied to a glass substrate (70) using a spin coater.
59, manufactured by Corning Incorporated) and 8 on a hot plate
It was dried at 0 ° C. for 1 minute. When the film thickness of the dried resist was measured by a stylus-type film thickness meter (α-step, manufactured by Tencor), it was 1.5 μm for the red, blue and green resists and 1 μm for the black resist. Next, this sample was image-exposed through a mask with a high-pressure mercury lamp while changing the exposure amount. Temperature 25
The resist was immersed and developed in a 0.05% aqueous solution of potassium hydroxide at a temperature of 0.05% for 1 minute to obtain a resist pattern.

1. Sensitivity Sensitivity was defined as an exposure amount (appropriate exposure amount) at which a mask pattern of 20 μm could be formed according to dimensions. In other words, it indicates that a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount. 2. Resolution The minimum resolvable resist pattern size at an exposure dose that faithfully reproduces a 20 μm mask pattern was observed with a microscope at 200 × magnification. The resolution was 寸 法 when the minimum pattern dimension was 10 μ or less, and × when the minimum pattern dimension exceeded 10 μ.

3. Light-shielding property The optical density of the image area of the black resist was measured by Macbeth reflection densitometer TR927 (manufactured by Kolmorgun) (OD). The OD value is a numerical value indicating the light-shielding ability, and the larger the numerical value, the higher the light-shielding property. 4. Adhesion Adhesion was evaluated by a cellotape test (the cellotape was peeled off after the cellotape was stuck on the resist pattern).も の indicates that the resist pattern was not stripped, and x indicates that the resist pattern was only stripped.

5. Developability The non-image area was visually observed as it dissolved in the developer. Developability was evaluated as "O" when the non-image area was developed so as to be dissolved in the developer, and as "x" when the non-image area was not dissolved in the developer and was removed as a strip. The non-image area which is removed as a peeled piece remains in the developing solution as it is and is re-adhered to the substrate to cause a defect in the color filter, which is not suitable as a resist developing mode. The results are shown in Table 1.

[0053]

[Table 1]

The color filter formed by forming a black matrix on a glass substrate using the black resist prepared in the embodiment in the same manner as described above and then forming pixels using red, green, and blue resist inks has a high quality. It was of high quality with no color blur.

[0055]

The resist composition for a color filter of the present invention is excellent in sensitivity, developability, resolution and adhesion even when a large amount of pigment is blended, so that a high quality color filter can be produced with high productivity. be able to. Further, when used as a light-shielding resist, a resin black matrix having a thin film and high light-shielding properties can be formed, so that a color filter having advantages in cost, reflectance, environment, and the like can be easily produced.

Claims (11)

[Claims] 1. A photopolymerizable composition containing (a) a coloring material (b) a photopolymerization initiator (c) a polymerizable monomer, wherein (c) the polymerizable monomer has 3 to 4 ( A photopolymerizable composition for a color filter, which is a mixture of a (meth) acrylic monomer having at least five (meth) acrylic groups in the same molecule as a (meth) acrylic monomer having a (meth) acrylic group. 2. The photopolymerizable composition for a color filter according to claim 1, further comprising (d) a binder resin and (e) a solvent. 3. The (c) (meth) acrylic monomer having 3 to 4 (meth) acrylic groups is an acrylate of pentaerythritol, and (meth) acrylic having 5 or more (meth) acrylic groups. The monomer is an acrylate of dipentaerythritol.
3. The photopolymerizable composition for a color filter according to 2. 4. The photopolymerizable composition for a color filter according to claim 1, wherein the binder resin is an organic polymer having a side chain ethylenically unsaturated double bond. 5. The photopolymerizable composition for a color filter according to claim 1, wherein the binder resin is a copolymer having a side chain ethylenically unsaturated double bond, a carboxyl group and a hydroxyl group. 6. The binder resin according to claim 1, wherein the binder resin is a styrene-based copolymer having an ethylenically unsaturated double bond, a carboxyl group and a hydroxyl group, or an acrylic copolymer.
6. The photopolymerizable composition for a color filter according to 5. 7. The photopolymerizable composition for a color filter according to claim 1, wherein the photopolymerization initiator is a complex initiation system containing a biimidazole derivative. 8. The photopolymerizable composition for a color filter according to claim 1, wherein (a) the coloring material is at least one pigment selected from red, blue and green. 9. The photopolymerizable composition for a color filter according to claim 1, wherein (a) the coloring material is a black pigment. 10. A color filter having colored pixels formed on a transparent substrate by the composition according to claim 1. Description: 11. A color filter having a resin black matrix formed of the composition according to claim 9 on a transparent substrate.