JPH11323143A - Light-screening photosensitive resin composition and color filter prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a light-screening photosensitive resin compsn. which has a high light-screening capability and is excellent in sensitivity, developability, resolution, insulating properties, adhesive properties, etc., by incorporating a resin-coated carbon black and a surfactant into the same. SOLUTION: A carbon black coated with a resin, pref. an epoxy resin, and pref. having a total oxygen content of 15 mg/g or higher, a ratio of total oxygen content/specific surface area of 0.10 or higher, an ash content of 1.0 wt.% or lower, and a DBP absorption of 140 ml/100 g or lower and a surfactant, pref. a fluorine-base surfactant, are incorporated. If necessary, a binder resin [e.g. a resin obtd. by reacting a styrene-acrylic acid resin with (3,4-epoxycyclohexyl) methyl acrylate], an ethylenically unsatd. compd. (e.g. dipentaerythritol hexaacrylate), and a photopolymn. initiator (e.g. a benzophenone deriv.) are also incorporated. The resin-coated carbon black is incorporated in an amt. of 35-70 wt.% of the total solids.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-shielding material which can be suitably used in the production of color filters used in the production of optical color filters used in color televisions, liquid crystal display devices, solid-state imaging devices, cameras and the like. The present invention relates to an optical resin composition. More specifically, the present invention relates to a light-shielding photosensitive resin composition which has high light-shielding properties, electrical insulation properties, and is excellent in photosensitive properties such as coating properties, sensitivity, resolution, developability and the like, and is suitable for producing a black matrix.

[0002]

2. Description of the Related Art In the production of color filters for liquid crystal display devices, a production method using a photosensitive resin in which a pigment is dispersed has become mainstream because of its high productivity and excellent fine workability. Also, a manufacturing method using a light-shielding photosensitive resin is being studied earnestly. However, the formation of a black matrix by the pigment dispersion method requires that the light-shielding photosensitive resin, which is a material, be provided with inherently contradictory properties of light-shielding and photosensitive. For this reason, it is essential to balance the light-sensitive properties and the light-shielding properties, but it is extremely difficult to secure the coating properties, resolution, sensitivity, and developability while maintaining a practical level of light-shielding properties in the conventional technology. It was difficult.

On the other hand, in recent years, researches for improving display quality such as viewing angle, contrast, response speed and the like of a liquid crystal display device have been actively conducted, but such a display device has an insulating property to a black matrix. There is something to demand. It is difficult to impart insulation to a conventional metal or metal oxide black matrix, and a high-resistance resin black matrix is desired.
No. 8869 describes the use of resin-coated carbon black, but it is still in the sense that it has various properties such as applicability (surface uniformity), high light-shielding properties, adhesion, and resolution. Not satisfactory.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and is excellent in coating characteristics, sensitivity, developability, resolution, and other photosensitive characteristics while having high light-shielding properties. An object of the present invention is to provide a light-shielding photosensitive resin composition suitable for forming a black matrix.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a light-shielding photosensitive composition comprising (a) carbon black coated with a resin and (b) a surfactant. The present inventors have found that a resin composition can solve such an object, and have completed the present invention. That is, the gist of the present invention resides in a light-shielding photosensitive resin composition containing (a) carbon black coated with a resin and (b) a surfactant.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The light-shielding photosensitive resin composition of the present invention essentially contains components (a) and (b) described below, and is usually a photosensitive liquid in which carbon black coated with a resin is finely dispersed. Used as Hereinafter, each component will be described.

(A) Carbon Black Coated with Resin The carbon black to be coated with the resin is not particularly limited, but preferably the following carbon blacks (i) and (ii) are used. (I) It is preferable that the total acid amount is 15 mg / g or more and the total oxygen amount / specific surface area is 0.10 or more. Oxygen functional groups such as a hydroxyl group (-OH), a carbonyl group, and a carboxyl group (-COOH) are present on the particle surface of the carbon black, and the amount thereof greatly changes the resistance when blended in a resin or the like. Usually, the oxygen functional group is measured by a volatile component composition, and the amount of a hydroxyl group or a carbonyl group can be quantified as CO or the amount of a carboxyl group as CO ₂ . Total oxygen content is CO
And CO ₂ , and this total oxygen amount is 1
It is preferably at least 5 mg / g, more preferably at least 20 mg / g. Further, the value of the amount of oxygen per unit surface area divided by the specific surface area is preferably at least 0.10, and more preferably at least 0.15.

[0008] The volatile matter composition is determined by adding a fixed amount of dried carbon black to a heat-resistant sample tube and placing it in a 10 ^-2 mmHg
After the pressure was reduced to 950 ° C, it was installed in an electric furnace heated to 950 ° C.
Volatiles are desorbed for 30 minutes, the total amount is collected and mixed in a tank, and the composition and amount of the gas are measured by gas chromatography to calculate the CO ₂ / CO ratio (weight ratio) and the total oxygen amount / specific surface area. .

The specific surface area is measured by the BET method. That is, the amount of nitrogen adsorbed on carbon black was measured by a low-temperature nitrogen adsorption method using a low-temperature nitrogen adsorption apparatus "Sortopmatic 1800" (manufactured by Carlo Elba, Italy), and the amount was calculated by the multipoint method using the BET equation. Things.

(Ii) Carbon black having an ash content of 1.0% by weight or less and a DBP absorption of 140 ml / 100 g or less is preferred. The composition of the ash is an alkali metal such as Na, K and Ca, an alkaline earth metal, or the like, and carbon black containing these may not provide sufficient insulating properties. This is considered to be due to the fact that ionic conductive substances such as Na, K, and Ca have a large water absorption, so that the carbon black-resin composite has an increased absorbency, and as a result, the insulating property is reduced.

The reduction of the ionic conductive material can be achieved by examining the raw material oil at the time of producing carbon black, examining the spray water used at the time of quenching, examining additives, and the like. It can also be achieved by washing or pickling carbon black produced from a production furnace. Further, it can also be achieved by combining the examination of the raw materials, spray water, additives and the like at the time of the above production with washing with water, pickling and the like. The content of the ionic conductive substance present in the carbon black is represented by the amount of ash remaining when the carbon black is calcined at 750 ° C. in air for 4 to 6 hours.
The ash content of the carbon black in the composition of the present invention is preferably 1.0% by weight or less, more preferably 0.1% by weight.
5% by weight or less.

If the DBP absorption measured by JIS-K6221-A exceeds 140 ml / 100 g, the blackness of carbon black itself is reduced, and the density feeling when mixed and applied to a resin varnish for black matrix is sufficient. In addition, the viscosity of the paste increases, and a coating film having good smoothness may not be obtained. The DBP absorption amount is preferably 140 ml / 100 g or less, more preferably 120 ml / 100 g or less.

In the present invention, the resin to be coated is not particularly limited, but is preferably an epoxy resin from the viewpoint of electrical insulation, heat resistance, dispersibility, etc., and particularly a polyfunctional epoxy having two or more epoxy groups. Resins are preferably used. Such epoxy resins include 1) glycidylamine type epoxy resin 2) triphenylglycidylmethane type epoxy resin 3) tetraphenylglycidylmethane type epoxy resin 4) aminophenol type epoxy resin 5) diamide diphenylmethane type epoxy resin 6) phenol novolak Type epoxy resin 7) Orthocresol type epoxy resin 8) Bisphenol A novolak type epoxy resin etc. can be used.
About "Sumiepoxy" EL manufactured by Sumitomo Chemical Co., Ltd.
M-434, ELM-120, ELM-100 and the like. Regarding 2) to 8), taking a product of Yuka Shell Epoxy Co., Ltd. as an example, 2): “Epicoat” 1032H60, “Epicoat”
1032H50 3): “Epicoat” 1031 4): “Epicoat” 154, “Epicoat” 630 5): “Epicoat” 604 6): “Epicoat” 152 7): “Epicoat” 180S65 8): “Epicoat” 157S65, “Epicoat” Epicoat ”1
57S70 and the like.

The method of coating the carbon black with the resin is not particularly limited. For example, after adjusting the compounding amounts of the carbon black and the resin as appropriate, A resin solution in which the resin is dissolved in an organic solvent such as cyclohexanone, toluene, or xylene, and a solution in which carbon black is suspended in water are mixed and stirred, and after separating carbon black and water, water is removed. 1. a method in which the composition obtained by heating and kneading is formed into a sheet, pulverized, and then dried; A method of mixing and stirring a resin solution and a suspension prepared in the same manner as described above to granulate carbon black and a resin, and separating and heating the obtained granules to remove remaining organic solvent and water. 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in an organic solvent, carbon black is added, mixed and dried, and the solvent is removed to obtain a carboxylic acid-impregnated carbon black. 3. dry blending technique; The reactive monomer component and water constituting the resin to be coated are stirred at high speed to prepare a suspension, and after polymerization, the mixture is cooled to obtain a reactive group-containing resin from the polymer suspension. After the graft reaction with the group, cooling, pulverization, and the like can be given.

The amount of the resin coated on the carbon black is 1 to 40 watts based on the total amount of the carbon black and the resin.
t% is preferable, and if the amount is less than 1 wt%, only electric insulation, dispersibility, and dispersion stability similar to those of untreated carbon black may be obtained. On the other hand, when the content exceeds 40 wt%, the adhesiveness between the resins is strong, and the resin becomes a cluster-like lump, and the dispersion may not proceed. In the present invention, a hardening agent, a hardening accelerator, and the like can be used in combination with the resin at the time of resin coating.

(B) Surfactant As the surfactant, any known surfactant can be used, but a fluorine-based surfactant is preferable, and a long-chain fluorocarbon group as a hydrophobic group and a hydrophilic group as a hydrophilic group are used. A compound having a sulfonic acid group, a carboxyl group, or a salt thereof, for example, an alkali metal salt such as sodium or potassium, a quaternary ammonium salt, a polyethylene oxide group, or the like in a molecule. An anionic type, a cationic type, a nonionic type, or an amphoteric type Any type can be preferably used.

For example, fluorine surfactants described in JP-A-3-188153 can be used. If specifically indicated by a trade name, for example, 1) anionic type trade name Surflon S-111, S-112, S-113
(Made by Asahi Glass Co., Ltd.), trade name MegaFac F-110,
F-120, F-113, F-191 (all manufactured by Dai Nippon Ink Co., Ltd.), trade names F-Top EF-102, EF-10
3. EF-104, EF-112 (all manufactured by Shin-Akita Kasei Co., Ltd.) Trade name F-gent F-100, F-150 (all manufactured by Neos) Brand name Unidyne DS-101, DS
-102 (all manufactured by Daikin Industries, Ltd.)
C-95, FC-98, FC-128, FC-143,
FX-161 (Sumitomo 3M)

2) Cation type Surflon S-121 (trade name, manufactured by Asahi Glass Co., Ltd.), Megafac F-150 (trade name, manufactured by Dainippon Ink Co., Ltd.),
Product name F-top EF-221 (all manufactured by Shin-Akita Kasei)
Product name Aftergent F-300 (Neos)
Trade name Unidyne DS-202 (manufactured by Daikin Industries, Ltd.) trade name Florard FC-95, FC-134 (manufactured by Sumitomo 3M) 3) amphoteric type trade names Surflon S-131, S-132, S-133
(Made by Asahi Glass Co., Ltd.), trade name MegaFax FX-172
(Manufactured by Dainippon Ink and Chemicals, Inc.), trade name: F-Top EF-2
24 (all manufactured by Shin-Akita Chemical Co., Ltd.)
400 (manufactured by Neos) Product name Unidyne DS-30
1 (Daikin Industries, Ltd.)

4) Nonion type: Surflon S-141, S-145 (trade name, manufactured by Asahi Glass Co., Ltd.), Megafax F-141, F-144, trade name
F-528 (manufactured by Dainippon Ink), trade names F-Top EF-121, EF-122, (manufactured by Shin-Akita Kasei Co.) Tradenames F-gent F-200, F-251 (manufactured by Neos) Name Unidyne DS-401, DS
-402 (all manufactured by Daikin Industries, Ltd.)
C-170, FC-176 (manufactured by Sumitomo 3M) Others, MegaFax FX-170, FX-17
3 (Dai Nippon Ink Co., Ltd.) Florad FC-4
30, FC-431 (all manufactured by Sumitomo 3M) and the like.

Preferred amounts of the above-mentioned surfactants are as follows:
The content of the light-shielding photosensitive resin composition in a photosensitive solution obtained by mixing a solvent is preferably 0.01 to 5000 ppm. More preferably, it is in the range of 0.1 to 1000 ppm. If the ratio is out of the above range, pinholes, coating unevenness, electric insulation, etc. may be deteriorated.

In the present invention, a light-shielding photosensitive resin composition can be obtained by adding a photosensitive resin composition to the above-mentioned essential components. As a photosensitive resin composition, a photopolymerization system combining an ethylenically unsaturated double bond-containing compound and a photopolymerization initiator, a chemical amplification system combining a photoacid generator and a crosslinking agent, and an azide or diazo resin as a photosensitive material Known photosensitive resins such as the photosensitive resin used, a photodimerization type photosensitive resin such as cinnamic acid or chalcone, and a photosensitive resin obtained by combining naphthoquinonediazide and an alkali-soluble resin can be used. Among them, a photosensitive resin system in which a binder resin, an ethylenically unsaturated double bond-containing compound, and a photopolymerization initiator are combined is particularly preferred because of its excellent sensitivity, resolution, adhesion, and developability. It is.

The preferred components of the photopolymerizable photosensitive resin composition are described in more detail below. (Binder resin) The binder resin is not particularly limited, but is preferably a binder resin having a carboxyl group because it preferably has alkali developability.
(Meth) acrylic acid as such a binder resin,
Such as 2-succinoloyloxyethyl methacrylate, 2-maleynoloyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, maleic anhydride, itaconic anhydride and the like Homopolymer of unsaturated carboxylic acid compound or the above monomer and styrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Butyl acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonate, (meth) acrylic chloride, benzyl (meth) acryl Over DOO, hydroxyethyl (meth) acrylate, N- methylolacrylamide, N, N-
Copolymers obtained by copolymerizing non-carboxylic acid monomers such as dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethylacrylamide can be used. Further, a binder resin having an ethylenically unsaturated double bond in a part of the resin side chain by reacting a compound having an epoxy group and an ethylenically unsaturated double bond in the same molecule with the above resin is also preferably used. be able to. When a double bond is provided to the resin side chain, the curability, heat resistance, adhesion and the like are improved, and thus such a binder resin is preferable.

For example, a binder resin in which a side chain double bond is introduced into the above resin with glycidyl methacrylate, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, or the like is preferable. The weight average molecular weight in terms of polystyrene measured by GPC of the binder resin is preferably from 1,000 to 200,000. Below this, it is difficult to obtain a uniform coating film, and if it is too large, the developability decreases. In addition, the molecular weight distribution (Mw /
Mn) is preferably from 1.5 to 10. If the molecular weight and the molecular weight distribution are out of this range, problems tend to occur in synthetic pinholes, coating unevenness, developability, and the like. From the viewpoint of developability, a preferred content of the carboxyl group is 5 to 2 in terms of acid value.
00. Deviating from this, developability, surface curability,
Deterioration of the film strength is likely to occur.

(Ethylenically unsaturated double bond-containing compound)
Examples of the ethylenically unsaturated double bond-containing compound include various known compounds that can be polymerized by the action of a photopolymerization initiator, and are preferably (meth) acrylic monomers, and particularly preferably have a (meth) acryloyl group in the molecule. And at least two low-molecular compounds. For example, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. Compounds can be mentioned. In particular, compounds having three or more acryloyl groups in the molecule are preferable because of their excellent photocurability.

(Photopolymerization initiator) As the photopolymerization initiator,
The compound is not particularly limited as long as it is a compound capable of polymerizing an ethylenically unsaturated double bond by actinic rays. For example, 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, Halomethylated triazine derivatives such as 6-bis (trichloromethyl) -s-triazine, 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ β- (2'-benzofuryl) vinyl]-
1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 Halomethylated oxadiazole derivatives such as furyl-1,3,4-oxadiazole, 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'-methoxyphenyl)-
Imidazole derivatives such as 4,5-diphenylimidazole dimer and (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and benzoins such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether Alkyl ethers, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as 1-chloroanthraquinone, benzuanthrone derivatives, benzophenone,
Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-
Benzophenone derivatives such as carboxybenzophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- ( p-dodecylphenyl) ketone, 2-
Acetophenone derivatives such as methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone,
Thioxanthone derivatives such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like Benzoic acid ester derivatives, acridine derivatives such as 9-phenylacridine, 9- (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-
And titanocene derivatives such as (pyr-1-yl) -phenyl-1-yl. Among these photopolymerization initiators, at least a biimidazole derivative or a titanocene derivative is preferable because of particularly high polymerization efficiency.

Further, sensitizing dyes which are preferably used in combination with these photopolymerization initiators are described in, for example, JP-A-3-239703.
Coumarin compounds having a heterocyclic ring described in JP-A-5-289335, 3-ketocoumarin compounds described in JP-A-63-221110, JP-A-4-221958, JP-A-4-221. Xanthene dyes described in JP-A-219756, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, and JP-A-56-1
No. 66154, JP-A-59-56403, (p-dialkylaminobenzylidene) ketone, styryl dyes, sensitizing dyes having julolidyl group described in Japanese Patent Application No. 5-83588, Japanese Patent Application No. 7 And a diaminobenzene compound described in -10109.

Among these sensitizing dyes, particularly preferred are amino group-containing sensitizing dyes, and more specifically, compounds having an amino group and a phenyl group in the same molecule. Specific examples include, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'- Benzophenone-based compounds such as diaminobenzophenone and 3,4-diaminobenzophenone;
-(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-
P- such as diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) pyrimidine and 2- (p-diethylaminophenyl) pyrimidine Examples thereof include compounds containing a dialkylaminophenyl group.

The light-shielding photosensitive resin composition of the present invention is used as a photosensitive liquid by adding the above-mentioned resin-coated carbon black, a surfactant and the above-mentioned photosensitive resin composition, and usually further adding an organic solvent.

The solvent used for preparing the light-shielding photosensitive resin composition as a photosensitive solution is not particularly limited as long as it can disperse or dissolve each component. Examples thereof include diisopropyl ether, mineral spirit, and n-pentane. , Amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apco thinner ,
Butyl ether, diisobutyl ketone, methyl cyclohexene, methyl nonyl ketone, propyl ether, dodecane, 1 and N
o. 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, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamido 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 ether acetate, dipropylene glycol monoethyl Ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3
-Methoxypropionic acid, 3-ethoxypropionic acid,
Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-
Propyl methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-
Specific examples thereof include organic solvents such as butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, and 3-methyl-3-methoxybutyl acetate.

When the light-shielding photosensitive resin composition is formulated with the above-described components, the preferred proportions are (a) 30 to 70 parts by weight of the resin-coated carbon black, 5 to 50 parts by weight of the binder resin, The unsaturated double bond-containing compound is 5 to 30 parts by weight, the photopolymerization initiator is 1 to
20 parts by weight of the surfactant is in the range described above. Outside this range, developability, sensitivity, resolution, adhesion, durability, light-shielding properties, and the like are easily lost. The preferred range of the amount of the solvent varies depending on the coating method. However, when a spin coater that is currently used most is used, the concentration of the solid component is preferably in the range of 15 to 30 wt%. The component (a) is 35 to 70% by weight, more preferably 40 to 6% by weight based on the total solid content of the light-shielding photosensitive resin composition excluding the solvent.
It is preferable to contain 0% by weight in order to achieve high light-shielding properties.

Next, a method for preparing the light-shielding photosensitive resin composition of the present invention will be described. Resin-coated carbon black is usually dispersed using a dispersing machine such as a paint conditioner, a sand grinder, a ball mill, a roll mill, a bead building, a stone mill, a homogenizer, a two-roller, or a three-roller by adding a solvent, a dispersant, and the like in advance. To process.
By the dispersion treatment, the carbon black can be stably present in the photosensitive liquid in the form of fine particles, and the coating film properties, light-shielding properties, electrical insulation properties, photosensitive properties, and the like can be improved.

The preferable dispersion state can be determined by the dispersion particle size of the carbon black and the gloss of the dispersion ink. The preferred particle size is 1 μm or less, preferably 0.5 μm or less, more preferably 0.3 μm or less. This particle size can be measured by a laser Doppler type particle size measuring device. For gloss, see JIS Z 874
The 20 ° specular gloss value described in 1 is 100 or more, preferably 110 or more, and more preferably 120 or more.

As the solvent used at the time of dispersion, the same organic solvents as those described above can be used. Preferred dispersants are surfactants such as anions, nonions and cations.
Polymer dispersants such as acrylic resins, styrene resins, polyamides, urethane resins, and silicone resins are exemplified.
A particularly preferred dispersant is a polymer dispersant having a basic functional group. Specific examples include BYK-161, 162, 163, 164, 166, and BYK-161 manufactured by Big Chemie.
70, 182, Solsperse S3000 manufactured by Zeneca,
S9000, S17000, S20000, S2700
0, S24000, S26000, S28000 and the like.

When the dispersing ink is prepared, the mixing ratio is preferably in the range of 50 to 1000 parts by weight of the solvent and 2 to 100 parts by weight of the dispersant with respect to 100 parts by weight of the resin-coated carbon black.

A light-shielding photosensitive resin composition is obtained by blending a surfactant, a binder resin, a photopolymerization initiator, and a photosensitive component such as an ethylenically unsaturated double bond-containing compound into the dispersion ink thus obtained. Can be.

Next, a method for producing a color filter using the light-shielding photosensitive resin composition of the present invention will be described.
First, the light-shielding photosensitive resin composition of the present invention is applied on a transparent substrate using a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, a spray, etc., and dried. Put the photo mask,
A light-shielding black matrix image is formed by image exposure, development and, if necessary, heat curing or light curing through the photomask, and the same operation is repeated for each of the three colored red, green and blue photosensitive compositions. A color filter image is formed.

The light-shielding photosensitive resin composition of the present invention can be exposed and developed to form an image without providing an oxygen barrier layer such as polyvinyl alcohol. 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, polypropylene, polyolefin such as polyethylene,
Polycarbonate, polymethyl methacrylate, polysulfone thermoplastic sheet, epoxy resin,
Examples thereof include thermosetting plastic sheets such as polyester resin and 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 a corona discharge treatment, an ozone treatment, a thin film treatment of various polymers such as a silane coupling agent or 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.
Should be within the range.

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 the wavelength of the specific irradiation light is used, an optical filter can be used.

The developing treatment 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 are not preferable because they have environmental pollution, harm to humans, and danger of fire. The use of an alkali developing solution is preferred. Examples of such an alkaline developer include sodium carbonate,
An aqueous solution containing an inorganic alkali agent such as potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide or the like, or an organic alkali agent such as diethanolamine, triethanolamine or tetraalkylammonium hydroxide salt can be used. Alkaline developers include
If necessary, a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxylic acid group, or the like can be contained. In particular, a surfactant is preferably added because many of them have an effect of improving the developing property, the resolution and the background stain.

For example, as a surfactant for a developer,
Examples thereof include an anionic surfactant having a sodium naphthalene sulfonate group and a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a cationic surfactant having a tetraalkylammonium group. The developing method is not particularly limited, but is usually 10 to 50 ° C., preferably 15 to 50 ° C.
It is carried out at a development temperature of up to 45 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.

After the image formation, a heat curing treatment or a light curing treatment can be performed. The curing treatment is effective for increasing the strength of the resist film, and can improve heat resistance and chemical resistance.

[0043]

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 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, propylene glycol monomethyl ether acetate (PGMEA) 40 g was charged into the flask, and (3, 4
-Epoxycyclohexyl) methyl acrylate 7.6
g was dropped 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 a neutralization titration with KOH was performed, the acid value of the resin was 80 mg KOH /
g. Also, as a result of measuring the molecular weight by GPC,
The weight average molecular weight Mw is 8000 and the number average molecular weight Mn is 3
000, molecular weight distribution Mw / Mn was 27.

Synthesis Example-2 125 g of benzyl methacrylate, 25 of methacrylic acid
g, azobisisobutyronitrile, 375 g of ethanol
Was charged into a flask and reacted at reflux for 4 hours. The reaction solution was reprecipitated in water to obtain a resin. As a result of neutralization titration with KOH, the acid value of the resin was 105. Also,
As a result of measuring the molecular weight by GPC, the weight average molecular weight Mw
Was 36,000, the number average molecular weight Mn was 10,000, and the molecular weight distribution Mw / Mn was 3.6.

Preparation of Resin-Coated Carbon Black Carbon black was produced by a usual oil furnace method. However, ethylene bottom oil having a small content of Na, Ca, and S was used as a raw material oil, and coke oven gas was used for combustion. Further, pure water treated with an ion exchange resin was used as the reaction stopping water. The produced carbon black has an average particle size of 50 nm and a DBP oil absorption of 50 m.
1/100 g. 54 above carbon black
0 g together with 14500 g of pure water using a homomixer
The mixture was stirred at 000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container equipped with a screw-type stirrer, and about 1,000 r
Epoxy resin "Epicoat 630" while mixing at pm
600 g of toluene in which 60 g was dissolved was added little by little. In about 15 minutes, the entire amount of the carbon black dispersed in the water was transferred to the toluene side to form particles of about 1 mm. Next, after draining with a 60-mesh wire net, it was placed in a vacuum drier and dried at 70 ° C. for 7 hours to completely remove toluene and water. The amount of residual toluene in the obtained carbon black was 50 ppm, and the amount of water was 500 ppm.

Preparation of Carbon Black Dispersion Ink (1) Ink-1 (Resin Coated Carbon Black Ink) 50 parts by weight of the above resin coated carbon black, BYK
-182 (polymer dispersant manufactured by BYK-Chemie Co., Ltd.) was added in an amount of 5 parts by weight in terms of solid content, and propylene glycol monomethyl ether acetate was further added to adjust the dispersion so that the solid content concentration became 50 wt%. Dispensing 50 g of the dispersion by weight,
Premixing was performed by stirring well with a stirrer. Next, use a paint shaker at 25-45 ° C for 6 hours.
Time dispersion processing was performed. As the beads, zirconia beads having a diameter of 0.5 mm were used, and the same weight as the dispersion was added. After the dispersion, the beads and the dispersion were separated by a filter to obtain a dispersion ink. (2) Ink-2 (untreated carbon black ink) A carbon black ink was prepared in the same manner as ink-1 except that carbon black was changed to MA-220 (manufactured by Mitsubishi Chemical Corporation).

Examples 1 to 6 and Comparative Examples 1 to 2 Using the above-described carbon black-dispersed ink, add each component to the following compounding ratio as a solid content, stir and dissolve with a stirrer. A liquid was prepared.・ Binder resin (described in Table-1) 25g ・ Carbon black (described in Table-1) 50g ・ Acrylic monomer dipentaerythritol hexaacrylate 15g ・ Photopolymerization initiator Described in Table-1 ・ Solvent propylene glycol monomethyl ether acetate 300g ・ Polymer Dispersant BYK-182 (manufactured by BYK-Chemie) 5 g ・ Surfactant (described in Table 1)

Using the obtained light-shielding photosensitive resin liquid, a resist pattern was formed as described below, and the following items were evaluated. The light-shielding photosensitive resin solution was applied to a glass substrate (7059, manufactured by Corning) using a spin coater, and dried at 80 ° C. for 1 minute on a hot plate. The thickness of the dried resist was measured by a stylus-type film thickness meter (α-step, manufactured by Tencor Corporation) and found to be 1 μm. The sample was then image exposed through a mask with a high pressure mercury lamp. The resist pattern was obtained by immersion and development in a potassium hydroxide aqueous solution having a temperature of 25 ° C. and a concentration of 0.05%. Further, post-baking was performed in a convection oven at 200 ° C. for 30 minutes.

The coating properties coating, resist film striation by 200 power microscope of the surface after drying, pinholes were observed whether the projection or the like. Those with no striae and no pinholes were evaluated as good, and those with striae and pinholes were evaluated as poor. The sensitivity was defined as the exposure amount (appropriate exposure amount) at which a pattern having a sensitivity of 20 μm could be formed according to the mask dimensions. The resolving power was evaluated based on the minimum resist pattern size capable of forming an image. In addition, those which can reproduce a resist pattern of 15 μ or less were defined as having good resolution.

[0051]Light blocking Image area of resist pattern after development (hereinafter referred to as solid area)
Optical density (OD) of Macbeth reflection densitometer TR927
(Manufactured by Korgorgun). OD value is shaded
It is a numerical value that indicates the ability.
AndResistance values Table of resist solid part in an atmosphere of 25 ° C and 50% relative humidity
The sheet resistance was measured. Adhesion The solid part after development is cut with a cutter of 10 × 10
In a grid pattern, and adhere and peel the cellophane tape
The adhesion was evaluated. No resist at the resist part of the grid
When no peeling was observed, good adhesion was obtained.Shelf life Store the photosensitive solution at room temperature for 3 days and determine the sensitivity as above.
Therefore, those with a sensitivity change of 10% or less with respect to the initial sensitivity
I liked it.

[0052]

[Table 1]

As shown in Table 1, the light-shielding photosensitive resin composition of the present invention has excellent coating properties, image properties, insulating properties and light-shielding properties. The size of the color filter substrate has been increasing year by year for the purpose of increasing the size of the liquid crystal display element itself, improving productivity, and reducing the cost. I have. In particular, the light-shielding photosensitive composition of the present invention exhibits good coating characteristics even on such a large-sized substrate, and does not cause problems such as striations, pinholes, protrusions, and unevenness in film thickness at the peripheral portion of the substrate. For this reason, it is effective for realizing a large-sized liquid crystal display element, improving quality, and reducing costs. Actually, a color filter in which a black matrix is formed using the light-shielding photosensitive resin composition of the present invention and then an RGB pattern is sequentially formed has excellent light-shielding properties, pattern accuracy, defects, and the like. Display elements can improve display quality such as resolution and contrast

[0054]

As described above, the light-shielding photosensitive resin composition of the present invention is excellent in sensitivity, resolution, adhesiveness, preservability, and coating property, so that the resin black matrix of a color filter used in a liquid crystal display device can be formed with high precision. Can be formed. Further, since it has excellent electrical insulation properties, it can be applied to IPS type LCDs and STN type LCDs compatible with a wide viewing angle, and the display quality can be improved. Furthermore, since the manufacturing process and the color filter itself do not contain harmful substances, the danger to the human body and the environmental safety are improved.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 5/22 G02B 5/22 G03F 7/004 504 G03F 7/004 504 505 505 7/027 7/027 7/028 7/028 7/032 501 7/032 501 // C09D 5/00 C09D 5/00 C 5/32 5/32 7/12 7/12 Z 133/00 133/00

Claims (6)

[Claims] 1. A light-shielding photosensitive resin composition comprising (a) carbon black coated with a resin and (b) a surfactant. 2. The light-shielding photosensitive resin composition according to claim 1, wherein (a) the coating resin is an epoxy resin. 3. The light-shielding photosensitive resin composition according to claim 1, wherein the surfactant is a fluorinated surfactant. 4. The composition according to claim 1, which comprises a binder resin, an ethylenically unsaturated double bond-containing compound, and a photopolymerization initiator.
3. The light-shielding photosensitive resin composition according to any one of 3. 5. The light-shielding photosensitive resin composition according to claim 1, wherein the resin-coated carbon black contains 35 to 70% by weight based on the total solid content. 6. A color filter comprising a transparent substrate and a black matrix formed of the light-shielding photosensitive resin composition according to claim 1.