JP2000292920A - Radiation sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make suppressible the lowering of the performance of a liquid crystal display device due to the contamination of a liquid crystal by components and impurities contained in a radiation sensitive composition, and to obtain a liquid crystal display device having high reliability. SOLUTION: The radiation sensitive composition for a color filter contains a colorant, an alkali-soluble resin, a polyfunctional monomer and a photopolymerization initiator and has a contamination degree of <=0.15 calculated by the equation (contamination degree)=(X-Y)/X, wherein X is the voltage retentivity of a liquid crystal display device using a substrate obtained by forming an ITO film on a glass substrate and containing an injected nematic liquid crystal and Y is the voltage retentivity of a liquid crystal display device using a substrate obtained by forming an ITO film on a glass substrate after applying and baking the radiation sensitive composition on the substrate and containing an injected nematic liquid crystal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element and the like.

[0002]

2. Description of the Related Art Conventionally, as a method of manufacturing a color filter used in a color liquid crystal display device, a color image pickup tube element, etc., conventionally, a coating film of a radiation-sensitive resin is irradiated with radiation through a photomask (hereinafter referred to as "exposure"). ) To cure the exposed portion, and then perform a developing process to remove the unexposed portion of the coating film to form a pattern, and then dye (a dyeing method) or a coloring agent to the radiation-sensitive resin. A photolithography method or the like of performing a coating film formation, exposure, and development treatment in the same manner as described above using a composition in which is dispersed is known.In recent years, from the viewpoint of heat resistance and light resistance, a pigment is added to a colorant. A photolithography method using the used pigment-dispersed radiation-sensitive composition is generally employed. However, the radiation-sensitive composition used in the color filter, in addition to the colorant represented by the pigment, usually contains a pigment dispersant, various additives, and the like, and is included in these components and those components When the impurities are eluted or bleed into the liquid crystal, the voltage holding ratio is reduced, display unevenness is generated, alignment failure is caused, and the performance as a liquid crystal display element is reduced. In addition, such performance deterioration may be caused by impurities mixed into the radiation-sensitive composition for a color filter from the outside during a process until a color filter is formed. Therefore, there is a demand for the development of a technology capable of avoiding a decrease in the performance of a liquid crystal display element due to contamination of the liquid crystal by components and impurities contained in the radiation-sensitive composition for a color filter.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to contaminate a liquid crystal by components and impurities contained in a radiation-sensitive composition for a color filter. An object of the present invention is to provide a radiation-sensitive composition for a color filter, which can suppress a decrease in performance of a liquid crystal display element caused by the above and can provide a liquid crystal display element having high reliability.

[0004]

According to the present invention, the object is to provide (A) a colorant, (B) an alkali-soluble resin,
It contains (C) a polyfunctional monomer and (D) a photopolymerization initiator, and has an impurity residual degree defined by the following formula [I] of 0.15.
The radiation-sensitive composition for a color filter is characterized by the following: Impurity residualness = (XY) / X ... [I] (where X is an ITO film formed on one surface of a glass substrate) Is the voltage holding ratio at a measurement temperature of 60 ° C. and a frame period of 500 milliseconds of a liquid crystal display element in which a nematic liquid crystal is injected using the substrate obtained above, and Y is obtained by applying the radiation-sensitive composition on one surface of a glass substrate. After baking, further using a board of an ITO film was formed, the voltage holding ratio at a measurement temperature of 60 ° C. and the frame period 500 ms of the liquid crystal display device was injected the same nematic liquid crystal.)
Achieved by Here, the "ITO film" is an indium oxide film doped with tin oxide, and forms a transparent electrode of a liquid crystal display device.

Hereinafter, the present invention will be described in detail. (A) Colorant The colorant in the present invention is not particularly limited in color tone, and is appropriately selected depending on the use of the obtained color filter, and may be any of a pigment, a dye, and a natural pigment.
Since the color filter is required to have high-definition color development and heat resistance, as the colorant in the first invention, a colorant having a high color development property and a high heat resistance, particularly a colorant having a high thermal decomposition resistance is preferable, Usually, pigments, particularly preferably organic pigments, are used.

Examples of the organic pigment include a color index (CI; The Society of Dyers and Coloris).
Compounds which are classified as Pigment (published by ts Co., Ltd.), specifically, those having a color index (CI) number as shown below. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16,
CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI
Pigment Yellow 65, CI Pigment Yellow 7
1, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97,
CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, C.I.
I. Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, C.I.
Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, C.I.
CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, C.I.
Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, C.I.
I. Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, C.I.
I. Pigment Yellow 180, CI Pigment Yellow 185;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, C.I.
I. Pigment Orange 17, CI Pigment Orange 2
4, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49,
CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, C.I.
I. Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

[0008] CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 1
0, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI
Pigment Red 41, CI Pigment Red 42, C.I.
I. Pigment Red 48: 1, CI Pigment Red 4
8: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, C.I.
I. Pigment Red 49: 2, CI Pigment Red 5
0: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 58:
2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64:
1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, C.I.
I. Pigment Red 104, CI Pigment Red 10
5, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123,
CI Pigment Red 144, CI Pigment Red 1
46, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI
Pigment Red 170, CI Pigment Red 17
1, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179,
CI Pigment Red 180, CI Pigment Red 1
85, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI
Pigment Red 202, CI Pigment Red 20
6, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224,
CI Pigment Red 226, CI Pigment Red 2
42, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI
Pigment Red 265;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, C.I.
I. Pigment Blue 15: 6, CI Pigment Blue 6
0: CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7. These organic pigments can be used alone or in combination of two or more. The organic pigment can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

Specific examples of the inorganic pigment include, for example, titanium oxide, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, navy blue, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. These inorganic pigments can be used alone or in combination of two or more.

The colorant in the present invention can be used by modifying its particle surface with a polymer, if desired. Examples of the polymer that modifies the surface of the colorant particles include polymers described in JP-A-8-259876 and various commercially available polymers or oligomers for dispersing pigments. The colorant in the present invention can be used together with a dispersant, if desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, and polyoxyethylene n-nonyl. Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products), Mega Akku (Dainippon Ink & Chemicals Co., Ltd.
Manufactured), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflon (all manufactured by Asahi Glass Co., Ltd.), Dis
perbyk (manufactured by BYK Japan KK), Solsperse (manufactured by Seneca Corporation), and the like. These surfactants can be used alone or in combination of two or more. The amount of surfactant used is
Usually 50 parts by weight or less, based on 100 parts by weight of the coloring agent,
Preferably it is 30 parts by weight or less.

(B) Alkali-Soluble Resin As the alkali-soluble resin in the present invention, (A) a developer which acts as a binder with respect to a colorant and is used in a development step in producing a color filter; It is particularly preferable to use an alkali-soluble resin having a carboxyl group, as long as it has solubility in an alkali developing solution. Particularly, an ethylenically unsaturated resin having one or more carboxyl groups Monomer (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”) and another copolymerizable ethylenically unsaturated monomer (hereinafter simply referred to as “copolymerizable unsaturated monomer”)
That. (Hereinafter, simply referred to as “carboxyl group-containing copolymer”).

Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, crotonic acid,
unsaturated monocarboxylic acids such as α-chloroacrylic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Trihydric or higher unsaturated polycarboxylic acid or its anhydride; mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2) phthalate -Acryloyloxyethyl),
2 such as mono (2-methacryloyloxyethyl) phthalate
Mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids having a valency of equal to or higher than a polymer having a carboxyl group and a hydroxyl group at the terminal such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. Mono (meth) acrylates and the like can be mentioned. These carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

Examples of the copolymerizable unsaturated monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene and p-vinyltoluene.
Chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether,
aromatic vinyl compounds such as p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; indenes such as indene and 1-methylindene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-
Propyl acrylate, n-propyl methacrylate,
i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate,
3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2- Methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2
-Phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxy Dipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2
-Hydroxy-3-phenoxypropyl acrylate,
Unsaturated carboxylic esters such as 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; unsaturated acids such as glycidyl acrylate and glycidyl methacrylate Carboxylic acid glycidyl esters; vinyl carboxylate esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide Amides such as N, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; maleimide, N
Unsaturated imides such as -phenylmaleimide and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly And macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain such as n-butyl methacrylate and polysiloxane. These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

The carboxyl group-containing copolymer of the present invention contains acrylic acid and / or methacrylic acid as an essential component, and may optionally contain mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyl succinate). Loxyethyl), at least one member selected from the group consisting of ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.
A carboxyl group-containing unsaturated monomer component further containing a seed, styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, A copolymer with at least one member selected from the group consisting of N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter, referred to as “carboxyl group-containing copolymer (B1)”) is preferable.

Specific examples of the carboxyl group-containing copolymer (B1) include (meth) acrylic acid / benzyl (meth)
Acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth)
Acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer Polymer, methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic mono (2-
(Meth) acryloyloxyethyl) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monosuccinic acid (2- (meth) acryloyloxyethyl) / styrene / allyl ( (Meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide / glycerol mono (meth) acrylate copolymer (meth) acrylic acid / styrene / benzyl (meth) ) Acrylate / N-phenylmaleimide / glycerol mono (meth) acrylate / ω-carboxypolycacrolactone mono (meth) acrylate copolymer.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5
５０50% by weight, preferably 10-40% by weight. In this case, when the copolymerization ratio is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developing solution tends to decrease, while when it exceeds 50% by weight, the solubility in an alkali developing solution becomes poor. When developing with an alkaline developer, there is a possibility that the pixel may easily fall off from the substrate or the pixel surface may be roughened.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as "Mw") of the alkali-soluble resin measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in the present invention is preferably from 3,000 to 300, 000, and more preferably 5,000 to 100,000. In addition, the number average molecular weight in terms of polystyrene (hereinafter, referred to as “polycarbonate”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention.
It is called “Mn”. ) Is preferably from 3,000 to 6,0
000, and more preferably 5,000 to 25,000. By using such an alkali-soluble resin having a specific Mw or Mn, a radiation-sensitive composition excellent in developability can be obtained, whereby a pixel having a sharp pattern edge can be formed, During development, residues, background stains, film residues, and the like hardly occur on the unexposed portion of the substrate and the light-shielding layer. Further, the ratio of Mw and Mn of the alkali-soluble resin in the present invention (Mw /
Mn) is preferably 1 to 5, more preferably 1 to 4
It is. In the present invention, the alkali-soluble resins can be used alone or in combination of two or more.

The amount of the alkali-soluble resin used in the present invention is usually 10 parts by weight per 100 parts by weight of the colorant (A).
１，1,000 parts by weight, preferably 20-500 parts by weight. In this case, when the use amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability is reduced,
There is a risk that background contamination or film residue may occur on the unexposed portion of the substrate or on the light-shielding layer. On the other hand, if it exceeds 1,000 parts by weight, the concentration of the colorant relatively decreases, so that the desired color as a thin film It may be difficult to achieve the concentration.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds. Examples of polyfunctional monomers include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol; diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerin, trimethylol Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as propane, pentaerythritol and dipentaerythritol and modified products of dicarboxylic acids thereof; polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, spirane resins, etc. Oligoacrylate or oligomethacrylates;
Diacrylate or dimethacrylates of hydroxyl-terminated polymers such as hydroxy-terminated poly-1,3-butadiene, hydroxy-terminated polyisoprene, hydroxy-terminated polycaprolactone, and tris (2-acryloyloxyethyl) phosphate And tris (2-methacryloyloxyethyl) phosphate.

Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids thereof, specifically, trimethylolpropane triacrylate, trimethylolpropane Trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, the following formula ( 1)

[0024]

Embedded image

Compounds represented by the following formulas are preferred. In particular, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate have high pixel strength, excellent pixel surface smoothness, and unexposed areas. This is preferable in that background contamination and film residue hardly occur on the substrate and the light-shielding layer. In the present invention, the polyfunctional monomers can be used alone or in combination of two or more.

The amount of the polyfunctional monomer used in the present invention is based on 100 parts by weight of (B) the alkali-soluble resin.
Usually, it is 5 to 500 parts by weight, preferably 20 to 300 parts by weight. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to decrease, while if it exceeds 500 parts by weight, for example, alkali developability decreases In addition, background contamination, film residue, and the like tend to easily occur on the unexposed portion of the substrate or the light-shielding layer.

In the present invention, a part of the polyfunctional monomer may be replaced with a monofunctional monomer, if necessary. Examples of such a monofunctional monomer include carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers exemplified for the carboxyl group-containing copolymer, N-acryloyl morpholine, N- Methacryloylmorpholine, N-vinylpyrrolidone, N-vinyl-
In addition to ε-caprolactam, M-53 is commercially available.
00, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like. These monofunctional monomers can be used alone or in combination of two or more. The usage ratio of the monofunctional monomer is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the obtained pixel tend to decrease.

(D) Photopolymerization Initiator The photopolymerization initiator according to the present invention may be prepared by subjecting the polyfunctional monomer (C) and optionally the It is a compound capable of generating a polymerizable active species of the monofunctional monomer used. Such photopolymerization initiators include, for example, acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds And the like. In the present invention, the photopolymerization initiator can be used alone or as a mixture of two or more, and as the photopolymerization initiator in the present invention, an acetophenone-based compound, a biimidazole-based compound and a triazine-based compound are used. At least one selected from the group is preferred.

In the present invention, the photopolymerization initiator is generally used in an amount of 0.01 to 100 parts by weight of the total of the polyfunctional monomer (C) and the monofunctional monomer. 80 parts by weight, preferably 1 to 60 parts by weight. In this case, if the amount of the photopolymerization initiator is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel array in which a pixel pattern is arranged according to a predetermined arrangement, On the other hand, if it exceeds 80 parts by weight, the formed pixels tend to fall off the substrate during development.

Among the preferred photopolymerization initiators in the present invention, specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- ( Methylthio) phenyl]
-2-morpholinopropanone-1, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
Butanone-1, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one and the like can be mentioned. Among these acetophenone-based compounds, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 is particularly preferred. The acetophenone-based compound,
They can be used alone or in combination of two or more.

In the present invention, when an acetophenone-based compound is used as a photopolymerization initiator, the amount used is (C)
Usually, 0.01 to 80 parts by weight, preferably 1 to 100 parts by weight of the total of the polyfunctional monomer and the monofunctional monomer.
６０60 parts by weight, more preferably 1-30 parts by weight. In this case, the amount of the acetophenone-based compound used is 0.
If the amount is less than 01 parts by weight, curing by exposure becomes insufficient,
It may be difficult to obtain a pixel array in which the pixel patterns are arranged according to a predetermined arrangement. On the other hand, if it exceeds 80 parts by weight, the formed pixels tend to fall off the substrate during development.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl)-
4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2-chlorophenyl) -4,4 ', 5,5'-
Tetrakis (4-ethoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl)-
4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2,4-dichlorophenyl) -4,4 ', 5
5'-tetrakis (4-ethoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2,4
-Dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-
Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4
-Methoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl)- 1,2′-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl)-
4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

2,2'-bis (2-bromophenyl)-
4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2-bromophenyl) -4,4 ', 5,5'-
Tetrakis (4-ethoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2,4-dibromophenyl)-
4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2,4-dibromophenyl) -4,4 ', 5
5'-tetrakis (4-ethoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2,4
-Dibromophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-
Biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4
-Methoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4,6-tribromophenyl)-
4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

2,2'-bis (2-cyanophenyl)-
4,4 ′, 5.5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′
-Bis (2-cyanophenyl) -4,4 ', 5.5'-
Tetrakis (4-ethoxycarbonylphenyl) -1,
2′-biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2-methylphenyl) -4,
4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-ethoxycarbonylphenyl) -1,2 '
-Biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2′-bis (2-ethylphenyl) -4,4 ′,
5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2
-Ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-ethylphenyl)-
4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,
2'-bis (2-phenylphenyl) -4,4 ', 5
5'-tetrakis (4-methoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, , 2'-bis (2-phenylphenyl)
-4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

2,2'-bis (2-chlorophenyl)-
4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2 '
-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 −
Bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,
4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-cyanophenyl) -4,4 ′,
5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dicyanophenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4', 5,5'-tetra Phenyl-
1,2′-biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenyl-
1,2′-biimidazole, 2,2′-bis (2,4-
Dimethylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5
5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-ethylphenyl) -4,4 ′,
5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-diethylphenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-triethylphenyl) -4,4', 5,5'-tetraphenyl −
1,2′-biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4
-Diphenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4',
5,5′-tetraphenyl-1,2′-biimidazole and the like can be mentioned.

Of these biimidazole compounds,
Preferred compounds are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′,
5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2
-Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-
Tetraphenyl-1,2'-biimidazole, 2,2 '
-Bis (2,4,6-trichlorophenyl) -4,
4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl)
-4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, and a more preferred compound is 2,2'-bis (2-chlorophenyl)-
4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2 '
-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, and particularly preferred compound is 2 , 2'-bis (2,4-dichlorophenyl)
-4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole. These biimidazole-based compounds have excellent solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, and have high sensitivity. High, no curing reaction occurs in the unexposed areas, so that the exposed coating film clearly shows a cured part insoluble in the developing solution and an uncured part having high solubility in the developing solution. As a result, a high-definition pixel array in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed. The biimidazole compounds can be used alone or in combination of two or more.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, the amount used is (C)
Usually, 0.01 to 40 parts by weight, preferably 1 to 100 parts by weight of the total of the polyfunctional monomer and the monofunctional monomer.
It is 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, the amount of the biimidazole-based compound used is 0.1.
If the amount is less than 01 parts by weight, curing by exposure becomes insufficient,
It may be difficult to obtain a pixel array in which the pixel patterns are arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, during development, the formed pixels may fall off the substrate of the formed pixels or the film on the pixel surface may be roughened. Tends to come easily.

-Hydrogen Donor- In the present invention, when a biimidazole compound is used as the photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination, since the sensitivity can be further improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound upon exposure. As the hydrogen donor in the first invention, a mercaptan compound defined below and an amine compound defined below are preferable. The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, and more preferably 1 to 2 mercapto groups directly bonded to the mother nucleus (hereinafter, referred to as “ Mercaptan hydrogen donor ”). The amine compound has a benzene ring or a heterocyclic ring as a mother nucleus, and has one or more amino groups, preferably 1 to 3, amino groups directly bonded to the mother nucleus.
, More preferably 1 to 2 compounds (hereinafter referred to as “amine-based hydrogen donor”). In addition, these hydrogen donors can have a mercapto group and an amino group simultaneously.

Hereinafter, these hydrogen donors will be described more specifically. The mercaptan-based hydrogen donor can have one or more benzene rings or one or more heterocycles, or can have both a benzene ring and a heterocycle. It may or may not be formed. Further, when the mercaptan-based hydrogen donor has two or more mercapto groups, as long as at least one free mercapto group remains, one or more of the remaining mercapto groups is substituted with an alkyl, aralkyl, or aryl group. And at least one more
As long as two free mercapto groups remain, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or a structural unit in which two sulfur atoms are bonded in a disulfide form Can be provided. further,
The mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a position other than the mercapto group. Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole,
2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4
-Thiadiazole, 2-mercapto-2,5-dimethylaminopyridine and the like. Among these mercaptan hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine-based hydrogen donor can have one or more benzene rings or one or more heterocycles, respectively.
Can have both a benzene ring and a heterocyclic ring,
When having two or more of these rings, a condensed ring may or may not be formed. Further, in the amine hydrogen donor, one or more of the amino groups may be substituted with an alkyl or substituted alkyl group, and at a position other than the amino group, a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group,
It may be substituted by a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like. Specific examples of such an amine hydrogen donor include 4,4 ′
-Bis (dimethylamino) benzophenone, 4,4'-
Bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like can be mentioned. Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable. The amine-based hydrogen donor has the same action as the component (E) described below.

In the present invention, the hydrogen donors can be used alone or as a mixture of two or more, but one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors are used in combination. This is preferable because the formed pixels are less likely to fall off the substrate during development, and the pixel strength and sensitivity are high. Specific examples of the combination of a mercaptan-based hydrogen donor and an amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'-bis ( Diethylamino) benzophenone,
2-mercaptobenzoxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (diethylamino)
Benzophenone and the like can be mentioned, and a more preferred combination is 2-mercaptobenzothiazole / 4,
4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, a particularly preferred combination is 2-mercaptobenzothiazole / 4,4′-
Bis (diethylamino) benzophenone. The weight ratio of the mercaptan hydrogen donor to the amine hydrogen donor in the combination of the mercaptan hydrogen donor and the amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 4. 3.

In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is usually based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. , 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight
Parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 part by weight,
The effect of improving sensitivity tends to decrease. On the other hand, when the amount exceeds 40 parts by weight, formed pixels tend to fall off the substrate during development.

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s
-Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (furan-2
-Yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2-
(3,4-dimethoxyphenyl) ethenyl] -4,6-
Bis (trichloromethyl) -s-triazine, 2- (4
-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

A compound represented by the following formula (2):

Embedded image

A compound represented by the following formula (3):

Embedded image

And triazine compounds having a halomethyl group. Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl)
Ethenyl] -4,6-bis (trichloromethyl) -s-
Preferred are triazine, the compound represented by the formula (2), the compound represented by the formula (3), and the like. The triazine compounds can be used alone or in combination of two or more.

In the present invention, when a triazine compound is used as a photopolymerization initiator, the amount used is usually based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. , 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight
Parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of the triazine-based compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel array in which pixel patterns are arranged according to a predetermined arrangement. If it exceeds 40 parts by weight, the formed pixels tend to fall off the substrate during development.

Further, in the present invention, a sensitizer, a curing accelerator, a polymer photocrosslinking / sensitizer and the like can be used together with the photopolymerization initiator. Examples of the sensitizer include 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 1,4-dimethylaminobenzoate, and 2,5-bis (4 ′ -Diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4
-Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like. These sensitizers can be used alone or in combination of two or more. The sensitizer has the same action as the component (E) described below. Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2,5-dimercapto-1,3.
Chain transfer agents such as 4-thiadiazole and 2-mercapto-4,6-dimethylaminopyridine can be exemplified. These curing accelerators can be used alone or in combination of two or more. Further, the polymer photocrosslinking / sensitizer is a polymer compound having at least one kind of functional group capable of acting as a crosslinking agent and / or a sensitizer upon exposure in a main chain and / or a side chain, Examples thereof include a condensate of 4-azidobenzaldehyde and polyvinyl alcohol, a condensate of 4-azidobenzaldehyde and a phenol novolak resin, and a homopolymer or copolymer of 4- (meth) acryloylphenyl cinnamate; , 4-polybutadiene, 1,2-polybutadiene and the like. These polymer photocrosslinking / sensitizers can be used alone or in combination of two or more. The total used amount of the sensitizer, the curing accelerator and the polymer photocrosslinking / sensitizer in the present invention is 100 photopolymerization initiators.
It is usually 300 parts by weight or less, preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to parts by weight.

(E) Component The radiation-sensitive composition for a color filter of the present invention includes:
(E) Epoxy group-containing compounds, oxetane ring-containing compounds, amino group-containing compounds, amino group-substituted carboxylic acid compounds, isocyanate group-containing compounds, crown ether compounds, other organic chelating agents, polyvinyl alcohol, polyethylene glycol or polyimide It is preferable that the composition further contains at least one component selected from the group consisting of an organic compound and an inorganic compound composed of an extender, a filler, or polyphosphoric acid (hereinafter, simply referred to as “component (E)”). That is, the radiation-sensitive composition for a color filter of the present invention contains the component (E), and thereby has a contamination degree defined by the above formula (I) (hereinafter, referred to as “contamination degree [I]”). It can be easily and reliably suppressed to 0.15 or less. The reason is not clear yet,
The component (E) is a component of the radiation-sensitive composition for a color filter, a pigment, a dispersant for a pigment, an additive, and the like, and impurities contained therein. Organic and inorganic substances that may adversely affect the liquid crystal, such as impurities (hereinafter collectively referred to as "contaminants") externally mixed into the radiation-sensitive composition for filters, and chemicals It is considered that the organic substance or the inorganic substance is hardly diffused into the liquid crystal as a result of binding, adsorption, or coordination, or a combination of two or more of these actions.

Among the components (E), examples of the epoxy group-containing compound include bisphenol A epoxy resin,
Hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester Resins, glycidylamine resins, epoxy resins such as epoxidized oils and brominated derivatives of these epoxy resins; aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives; butadiene Other epoxy group-containing organic compounds such as epoxidized (co) polymers, epoxidized (co) polymers of isoprene, (co) polymers of glycidyl (meth) acrylate, and (co) polymers of allyl glycidyl ether Molecular compounds and the like can be mentioned, and more specifically, the following formulas (4) to (11) In and represented by compound include triglycidyl isocyanurate.

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image (However, i is an integer of 1 to 300.)

[0055]

Embedded image (However, i is an integer of 1 to 300.)

[0056]

Embedded image (However, each R independently represents a hydrogen atom, a halogen atom or a methyl group, and j is an integer of 1 to 100.)

[0057]

Embedded image

[0058]

Embedded image (However, k is an integer of 0 to 50.)

Examples of the oxetane ring-containing compound include oxetane, 3-methyloxetane, 3-ethyloxetane, 3-n-propyloxetane, and 3-n-
Butyl oxetane, 3-vinyl oxetane, 3-allyl oxetane, 3-benzyl oxetane, 3,3-dimethyl oxetane, 3,3-diethyl oxetane, 3-methyl-3-ethyl oxetane, 3-methyl-3-n-propyl Examples thereof include an oxetane ring-containing organic low molecular weight compound such as oxetane and 3-methyl-3-n-butyloxetane, and an oxetane ring-containing organic high molecular compound such as a (co) polymer of 3-vinyloxetane.

Examples of the amino group-containing compound (including a chelating agent comprising an amino group-containing compound) include n-propylamine, i-propylamine, n-butylamine, i-butylamine and t-butylamine. , N
-Pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-
Decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, o-methylcyclohexylamine, m-methylcyclohexylamine, p-methylcyclohexylamine, o-ethylcyclohexylamine, m-ethylcyclohexylamine, p-ethylcyclohexyl Mono (cyclo) alkylamines such as amines; methylethylamine, diethylamine, methyl n-
Propylamine, ethyl n-propylamine, di-n-
Propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, Di (cyclo) alkylamines such as dicyclohexylamine; dimethylethylamine, methyldiethylamine, triethylamine, dimethyln-propylamine, diethyln-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-
n-propylamine, tri-i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-
t-butylamine, tri-n-pentylamine, tri-
n-hexylamine, dimethylcyclohexylamine,
Tri (cyclo) alkylamines such as diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

2-aminoethanol, 3-amino-1-
Propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-
Mono (cyclo) alkanolamines such as cyclohexanol; diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, Di-n-hexanolamine, bis (4
Di (cyclo) alkanolamines such as -cyclohexanol) amine; triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n Tri (cyclo) alkanolamines such as -pentanolamine, tri-n-hexanolamine and tris (4-cyclohexanol) amine;

3-amino-1,2-propanediol,
2-amino-1,3-propanediol, 4-amino-
1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3
Amino (cyclo) such as -dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol
Alkanediols; 1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexane Methanol, 4
Amino-containing cycloalkanemethanols such as diethylaminocyclohexanemethanol;

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, pt- Butylaniline, 1-naphthylamine, 2-naphthylamine, N, N
-Dimethylaniline, N, N-diethylaniline, p-
Aromatic amines such as methyl-N, N-dimethylaniline; aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol Kind;
o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-
Aminophenols such as diethylaminophenol; low molecular weight compounds containing amino groups such as chelating agents containing amino groups such as ethylenediamine, phenanthroline, bipyridine, oxine and phthalocyanine; polyvinylamine;
A (co) polymer of aminoethyl (meth) acrylate,
Examples thereof include an amino group-containing organic polymer compound such as a (co) polymer of 2-dimethylaminoethyl (meth) acrylate, an aminated (co) polymer of styrene, or an aminomethylated product.

Examples of the amino-substituted carboxylic acid compound (including a chelating agent comprising an amino-substituted carboxylic acid compound) include β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, and 4-aminobutyric acid. Butyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid Amino-substituted aliphatic carboxylic acids or amino-substituted alicyclic carboxylic acids such as m-aminobenzoic acid, p-aminobenzoic acid,
Amino group-substituted aromatic carboxylic acids such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; amino-substituted carboxylic acid low-molecular compounds such as chelating agents comprising amino-substituted carboxylic compounds such as ethylenediaminetetraacetic acid and glycine And organic polymer compounds containing an amino group and a carboxyl group, such as a (meth) acrylic acid / 2-amino (meth) acrylate copolymer.

Examples of the isocyanate group-containing compound include ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,
Aliphatic polyisocyanate compounds such as 6-diisocyanate and dodecamethylene-1,12-diisocyanate;
Cyclopentane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-
1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexane-
Alicyclic polyisocyanate compounds of 1,3,5-triisocyanate, dicyclohexylmethane-2,4,2'-triisocyanate, dicyclohexylmethane-2,4,4'-triisocyanate;

Phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 1-ethoxyphenylene-2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3- Xylylene diisocyanate, 1,4-
Xylylene diisocyanate, biphenylene-4,4 '
-Diisocyanate, 3,3'-dimethoxybiphenylene-4,4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate,
3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, naphthylene-1,5-diisocyanate, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, diphenylmethane-2, 5,4′-triisocyanate,
Triphenylmethane-2,4 ', 4 "-triisocyanate, triphenylmethane-4,4', 4" -triisocyanate, diphenylmethane-2,4,2 ', 4'-
Tetraisocyanate, diphenylmethane-2,5
Aromatic polyisocyanate compounds such as 2 ', 5'-tetraisocyanate; terminal isocyanate prepolymers obtained by reacting a stoichiometric excess of these polyisocyanate compounds with a bifunctional or higher polyfunctional active hydrogen-containing compound Isocyanate group-containing low molecular compounds such as,
Methyl (meth) acrylate / styrene / vinyl isocyanate copolymer, (meth) acrylic acid / styrene / 2-
(Meth) acryloyloxyethyl isocyanate copolymer, isocyanate group-containing organic polymer compound such as polyurethane obtained by polycondensation of toluene diisocyanate and diethylene glycol, and the like.

Examples of the crown ether compound include 12-crown-4, 15-crown-5, and 18-crown-5.
Crown-6, dibenzo-24-crown-8, perhydrodibenzo-24-crown-8 and the like can be mentioned. Examples of the organic chelating agent other than the above include citric acid, dimethylglyoxime, acetylacetone, polyhydrazide and the like. The component (E) composed of an organic compound other than the amino group-substituted carboxylic acid compound can have two or more groups selected from the group consisting of an epoxy group, an oxetane ring, an amino group and an isocyanate group.

Examples of the extender include barium sulfate, barium carbonate, calcium carbonate, basic magnesium carbonate, silica, alumina, gloss white, satan white, and the like.
Hydrotalcite and the like can be mentioned. Examples of the filler include activated carbon, calcium chloride, and the like.

As the component (E) in the present invention, an epoxy group-containing compound, an oxetane ring-containing compound, and an organic chelating agent are preferable. Among the preferred components (E),
As the epoxy group-containing compound, a compound represented by the formula (4), (5), (6) or (10) is more preferable, and a compound represented by the formula (5) is particularly preferable. . Further, as the oxetane ring-containing compound, a (co) polymer of oxetane, 3-vinyloxetane, 3-benzyloxetane, 3-vinyloxetane, and the like are more preferable. Further, as the organic chelating agent, ethylenediaminetetraacetic acid, bipyridine, citric acid, dimethylglyoxydim and the like are more preferable, and ethylenediaminetetraacetic acid is particularly preferable. In addition, polyvinylamine, isocyanate group-containing organic polymer compounds, polyimides, and the like,
It is preferably used as the component (E). The Mw of the component (E) composed of an organic polymer compound is not particularly limited, but is usually 1,000 to 500,000,
Preferably it is 3,000-100,000.

The amount of component (E) used in the present invention is generally 0.1 to 50 parts by weight, preferably 0.2 to 30 parts by weight, based on 100 parts by weight of the total solids in the radiation-sensitive composition. Parts, more preferably 0.3 to 20 parts by weight.

The degree of contamination [I] of the radiation-sensitive composition for a color filter in the present invention is 0.15 or less, preferably 0.10 or less, more preferably 0.08 or less, and particularly preferably 0.05 or less. is there. This pollution degree [I]
(E) It depends on the kind and use amount of the component and the kind and use amount of each component constituting the radiation-sensitive composition for a color filter. Is achieved.

Additives The radiation-sensitive composition for a color filter of the present invention may contain various additives, if necessary. In the radiation-sensitive composition for a color filter of the present invention, (E)
When the component contains an oxetane ring-containing compound, (B)
When the alkali-soluble resin has a carboxyl group, the composition can be cross-linked (cured) by simply heating the composition. A crosslinking (curing) agent capable of ring-opening polymerization of the compound may be further contained.

Examples of the crosslinking (curing) agent include polycarboxylic acids, polycarboxylic anhydrides, and radiation-sensitive acid generators that generate an acid upon exposure.
Examples of the polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid,
Aromatic polycarboxylic acids such as 3,3 ′, 4,4′-benzophenonetetracarboxylic acid; succinic acid, glutaric acid,
Aliphatic polycarboxylic acids such as adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, and itaconic acid; hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,2 Examples include alicyclic polycarboxylic acids such as 4-cyclohexanetricarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.

Examples of the polycarboxylic anhydrides include aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and benzophenonetetracarboxylic anhydride; Acid, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride,
Aliphatic or alicyclic dicarboxylic anhydrides such as tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hymic anhydride, and nadic anhydride;
3,4-butanetetracarboxylic dianhydride, 1,2,2
Aliphatic polycarboxylic dianhydrides or alicyclic polycarboxylic dianhydrides such as 3,4-cyclopentanetetracarboxylic dianhydride; esters such as ethylene glycol bis trimellitate and glycerin tristrimellitate Examples of the acid anhydride include a group-containing acid anhydride.

As the crosslinking (curing) agent, a commercially available epoxy resin curing agent composed of a carboxylic anhydride can also be suitably used. For example, a trade name of Adeka Hardener EH-700 (Asahi Denka Kogyo Co., Ltd.) Co., Ltd.), Rikka Seed HH, MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), Epikinia 126, YH-306, DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like.

Examples of the radiation-sensitive acid generator include:
4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate triphenylsulfonium p -Onium salts such as toluene-sulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate.

Among these crosslinking (curing) agents, aromatic polycarboxylic acids, aromatic polycarboxylic anhydrides, onium salts and the like are preferable. The crosslinking (curing) agents can be used alone or in combination of two or more. The amount of the crosslinking (curing) agent used is (B) alkali-soluble resin 10
It is usually at most 25 parts by weight, preferably at most 15 parts by weight, based on 0 parts by weight. In this case, if the amount of the cross-linking (curing) agent exceeds 25 parts by weight, the formed pixels may easily fall off the substrate during development.

Examples of additives other than the crosslinking (curing) agent include, for example, a dispersing aid such as a blue pigment derivative or a yellow pigment derivative such as a copper phthalocyanine derivative; a filler other than the above such as glass; Acrylate) and other polymer additives; nonionic, cationic, anionic surfactants; vinyltrimethoxysilane;
Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-
Aminopropyl methyl dimethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3
4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane,
Adhesion promoters such as 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-t-butylphenol);
Antioxidants such as 2,6-di-t-butylphenol; 2
UV absorbers such as-(3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; aggregation inhibitors such as sodium polyacrylate; 1,1'-azobis ( Cyclohexane-1-carbonitrile), 2-phenylazo-4
Thermal radical generators such as -methoxy-2,4-dimethylvaleronitrile;

Solvent The radiation-sensitive composition for a color filter of the present invention contains the above components (A) to (D) as essential components, preferably contains the above component (E), and optionally contains the above additive components. However, it is preferably prepared as a liquid composition by mixing a solvent. As the solvent, as long as it disperses or dissolves the components (A) to (E) and the additive components constituting the radiation-sensitive composition, and does not react with these components and has appropriate volatility. Can be appropriately selected and used. Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-ethyl. n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n -Butyl ether, dipropylene glycol monomethyl acrylate Le, dipropylene glycol monoethyl ether, dipropylene glycol mono -
n-propyl ether, dipropylene glycol mono-
(Poly) alkylene glycol monoalkyl ethers such as n-butyl ether, tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; and other such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran Ether compounds; methyl ethyl ketone,
Ketones such as cyclohexanone, 2-heptanone and 3-heptanone; methyl 2-hydroxypropionate;
Alkyl lactates such as ethyl hydroxypropionate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate; -Methyl ethoxypropionate, ethyl 3-ethoxypropionate,
Ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, acetic acid n-butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate,
Methyl pyruvate, ethyl pyruvate, n-pyruvate
Propyl, methyl acetoacetate, ethyl acetoacetate, 2-
Other esters such as ethyl oxobutanoate; toluene,
Aromatic hydrocarbons such as xylene; amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide;

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, from the viewpoints of solubility, pigment dispersibility, coatability and the like.
Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl acetate, 3-
Methyl-3-methoxybutyl propionate, n-acetic acid
Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-butyrate
Preferred are propyl, n-butyl butyrate, ethyl pyruvate, toluene, N-methylpyrrolidone and the like. The solvent is
They can be used alone or in combination of two or more.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, High boiling solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate can also be used in combination.
The high boiling point solvents can be used alone or in combination of two or more.

The amount of the solvent used is not particularly limited, but from the viewpoint of the coating properties and stability of the radiation-sensitive composition obtained, the total concentration of each component excluding the solvent in the composition solution is preferably , Preferably 5 to 50% by weight, more preferably 1 to 50% by weight.
An amount of 0 to 40% by weight is desirable.

Method for Forming a Color Filter Next, a method for forming a color filter using the radiation-sensitive composition for a color filter of the present invention will be described. First, a light-shielding layer is formed so as to partition a portion where a pixel pattern is formed on the surface of a transparent substrate, and on this substrate,
For example, after applying a liquid composition of a radiation-sensitive composition in which a red organic pigment is dispersed, prebaking is performed to evaporate the solvent, thereby forming a coating film. Next, after this coating film is exposed through a photomask, a developing process is performed with an alkali developing solution, and an unexposed portion of the coating film is dissolved and removed, whereby a pixel array in which red pixels are arranged in a predetermined pattern. To form Thereafter, using a liquid composition of each radiation-sensitive composition in which a green or blue organic pigment is dispersed sequentially, in the same manner as described above, application of each composition, pre-baking,
By performing exposure and development processing, a color filter in which pixel arrays of three primary colors of red, green, and blue are formed on the same substrate is obtained. Examples of the transparent substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, and polyimide. These transparent substrates may be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum deposition, if desired. When applying the radiation-sensitive composition for a color filter of the present invention to a transparent substrate, an appropriate coating method such as spin coating, casting coating, and roll coating can be employed. The coating thickness is usually 0.1 to 10 μm, preferably 0.1 to 10 μm, as the thickness after drying.
2 to 6.5 μm. As the radiation used when forming the color filter, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-ray, or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. Exposure energy amount is preferably 1 to 1000 mJ / cm
² Examples of the alkaline developer used for the development treatment include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, and 1,8-diazabicyclo- [5.4.
0] -7-undecene, 1,5-diazabicyclo-
An aqueous solution such as [4.3.0] -5-nonene is preferred. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkali developer. In addition, after the development processing with an alkali developer,
Usually, wash with water. As a developing method using an alkali developing solution, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method, or the like can be applied. preferable.
The color filter thus formed can be used very suitably for a color liquid crystal display device, a color image pickup tube element, a color sensor and the like.

The color filter thus formed from the radiation-sensitive composition for a color filter of the present invention does not cause a reduction in voltage holding ratio, image sticking or poor orientation, and has an excellent display state after energization. Thus, a highly reliable liquid crystal display device can be provided.

[0085]

BEST MODE FOR CARRYING OUT THE INVENTION The radiation-sensitive composition for a color filter of the present invention comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. Is an essential component, and preferably contains the component (E). Particularly preferred examples of the composition include the following (A) to (I). (A) Component (B) is a carboxyl group-containing copolymer (B
(D) A radiation-sensitive composition for a color filter, wherein the photopolymerization initiator comprises at least one selected from the group consisting of an acetophenone-based compound, a biimidazole-based compound, and a triazine-based compound. (B) Component (B) is a carboxyl group-containing copolymer (B
(1) A radiation-sensitive composition for a color filter, wherein (D) the photopolymerization initiator contains a biimidazole compound and a hydrogen donor. (C) The radiation-sensitive composition for a color filter according to (b), wherein the hydrogen donor is a mercaptan-based hydrogen donor and / or an amine-based hydrogen donor. (D) at least one component (D) selected from the group consisting of acetophenone compounds and triazine compounds;
The radiation-sensitive composition for a color filter according to the above (b) or (c), comprising a seed. (E) The component (D) further comprises at least one selected from the group consisting of a sensitizer, a curing accelerator and a polymer photocrosslinking / sensitizer, (a), (b), (c) or (d). A) a radiation-sensitive composition for a color filter. (F) The component (C) wherein the component (C) contains at least one selected from the group consisting of trimethylolpropane triacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
(B) The radiation-sensitive composition for a color filter according to (c), (d) or (e). (G) The component (E) wherein the component (E) contains at least one selected from the group consisting of an epoxy group-containing compound, an oxetane ring-containing compound, a chelating agent, polyvinylamine, an isocyanate group-containing organic polymer compound, and polyimide.
(B), (c), (d), (e) or (f), a radiation-sensitive composition for a color filter. (H) The component (A) wherein the component (A) is an organic pigment.
(B), (c), (d), (e), (f) or (g)
Radiation-sensitive composition for color filters. (I) The above (A), (B), (C), (D), (E) wherein the degree of contamination [I] is 0.10 or less, more preferably 0.08 or less, particularly preferably 0.05 or less. ), (F),
(G) or (h) the radiation-sensitive composition for a color filter.

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments.

EXAMPLES In Examples and Comparative Examples, the voltage holding ratio,
The degree of contamination, burn-in, and the state of display after energization were evaluated as follows. Evaluation of voltage holding ratio Liquid crystal: A nematic liquid crystal (trade name: ZLI-5081, manufactured by Merck Japan Ltd.) composed of a fluorobiphenyl derivative was used. Production of liquid crystal display element: 1 cm ² patterned on one side of a glass substrate
Is formed, a commercially available liquid crystal aligning agent for active matrix is applied on the ITO film by using a spinner, and then dried at 180 ° C. for 1 hour to obtain a film thickness of 8
A 00 ° coating was formed. After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each comparative example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After forming an ITO film (continuous film) on one side of a glass substrate, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. Next, a rubbing treatment was performed on the surface of the coating film on each of the substrates obtained by using a rubbing machine provided with a roll wound with a rayon cloth to form a liquid crystal alignment film. The rubbing conditions at that time were as follows:
rpm, the stage moving speed was 3 cm / sec, and the push-in length of the hair foot was 0.4 mm. Of the substrates on which the liquid crystal alignment film has been formed in this manner, or each of the substrates that have been subjected to the processing, are combined with the substrates that have undergone the processing to form a pair, and the outer edge of the two substrates is provided for each pair. After applying an epoxy resin-based adhesive containing 18 μm diameter aluminum oxide spheres by screen printing, the two substrates are opposed to each other with a gap between them so that the rubbing directions of the liquid crystal alignment films are reversed. Then, the substrates were pressed so that the outer edges of the substrates were in contact with each other to cure the adhesive. Next, for each set, a nematic liquid crystal “ZLI-5081” is injected and filled into a cell gap defined by the inner surface of the two substrates and the cured layer of the adhesive, and then the injection hole is sealed. A liquid crystal cell was manufactured. Thereafter, a polarizing plate was attached to the outer surface of the liquid crystal cell so that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film on each substrate, thereby producing a liquid crystal display device. Measurement of voltage holding ratio: After applying a voltage of 5 V DC for 6 × 10 ⁻⁵ seconds to the liquid crystal display element held in a thermostat at 60 ° C., a voltage 0.5 seconds after the application of the voltage was released. The holding ratio was measured using a voltage holding ratio measuring device “VHR-1” (trade name,
(Manufactured by Toyo Corporation). Evaluation of Pollution Degree From the voltage holding ratio measured as described above, the pollution degree was calculated by the above formula [I].

Evaluation of Burn-in Liquid Crystal: A nematic liquid crystal (trade name: ZLI-5081, manufactured by Merck Japan Ltd.) composed of a fluorobiphenyl derivative was used. Production of liquid crystal display element: 1 cm ² patterned on one side of a glass substrate
After forming an ITO film, a commercially available liquid crystal aligning agent for active matrix was applied on the ITO film by using a spinner, and then dried at 180 ° C. for 1 hour to form a film having a thickness of 6 μm.
A 00 ° coating was formed. After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After a patterned 1 cm ² ITO film was formed on a color filter formed using the liquid composition of each comparative example, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. . After forming an ITO film (continuous film) on one side of a glass substrate, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as described above. Next, a rubbing treatment was performed on the surface of the coating film on each of the substrates obtained by using a rubbing machine provided with a roll wound with a rayon cloth to form a liquid crystal alignment film. The rubbing conditions at that time were as follows:
rpm, the stage moving speed was 3 cm / sec, and the push-in length of the hair foot was 0.4 mm. Of the substrates on which the liquid crystal alignment film has been formed in this manner, or each of the substrates that have been subjected to the processing, are combined with the substrates that have undergone the processing to form a pair, and the outer edge of the two substrates for each set After applying an epoxy resin-based adhesive containing a silica gel columnar spacer with a diameter of 5.5 μm to the part by screen printing, the gap between the two substrates is adjusted so that the rubbing directions of the liquid crystal alignment films cross at 90 degrees. The substrates were opened and opposed to each other, and were pressed so that the outer edges of the substrates were in contact with each other to cure the adhesive. Next, for each set, a nematic liquid crystal “ZLI-5081” is injected and filled into a cell gap defined by the inner surface of the two substrates and the cured layer of the adhesive, and then the injection hole is sealed. A liquid crystal cell was manufactured. Thereafter, a polarizing plate was attached to the outer surface of the liquid crystal cell so that the polarization direction of the polarizing plate coincided with the rubbing direction of the liquid crystal alignment film on each substrate, thereby producing a liquid crystal display device. Burn-in evaluation method: Function generator WAVE on liquid crystal display
FACTRY (NF ELECTRONIC INSTRUMENT) is connected,
A rectangular wave voltage of AC 3 V and DC 1 V is applied, and the liquid crystal display element is heated at 70 ° C. for 1 hour in that state. The liquid crystal display element after heating is turned off for 5
After cooling for 30 minutes, a rectangular wave voltage of 30 Hz and a halftone voltage is applied by the function generator. Using an LCD EVALUATION SYSTEM (Photal), the flicker waveform obtained from the flicker appearance pulse data related to the display of the liquid crystal display element was converted to an oscilloscope 5460.
0A OSCILLOSCOPE (made by HEWLETT PACKARD)
FFT analyzer R9211C FFT SERVO ANALYZER (ADVANTES
(Company T) to measure the flicker strength. An offset voltage is applied by the function generator, and an offset voltage at a point where the flicker waveform completely disappears is measured to obtain a flicker elimination voltage (that is, a burn-in removal voltage). The image sticking is evaluated according to the following criteria. : Flicker erasing voltage is less than 50 mV ×: Flicker erasing voltage is 50 mV or more (Note) The degree of burn-in becomes more significant as the flicker erasing voltage becomes larger. Then, when the liquid crystal display element is used for a long time, burn-in occurs. The flicker erasing voltage is more preferably 20 mV or less.

Evaluation of display state after energization When manufacturing a liquid crystal display element, a color filter having a thickness of 2.0 μm was formed on one surface of the substrate before applying a liquid crystal aligning agent. After applying the alignment agent, a liquid crystal display device with a color filter was manufactured using the nematic liquid crystal “ZLI-5081” in the same manner as in the method of manufacturing the liquid crystal display device. Next, the liquid crystal display device was held in a thermostat at 100 ° C.
After energizing for months, observe the display state of the liquid crystal display element after the energization (the presence or absence of display unevenness) with the naked eye and a polarizing microscope,
Evaluation was made according to the following criteria. ○: No display unevenness ×: Display unevenness

Example 1 CI Pigment Red 177 was used as the component (A).
Parts by weight, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer as component (B) (copolymerization weight ratio = 25/65/10, Mw = 55,000)
50 parts by weight, 40 parts by weight of dipentaerythritol pentaacrylate as the component (C), 2,2 as the component (D)
2'-bis (2-chlorophenyl) -4,4 ', 5
5'-tetraphenyl-1,2'-biimidazole 10
Parts by weight, 10 parts by weight of 4,4'-bis (diethylamino) benzophenone, 15 parts by weight of the epoxy group-containing compound represented by the formula (5) as the component (E), and ethylene glycol monoethyl ether acetate 8 as a solvent
The liquid composition was prepared by mixing 00 parts by weight. Then, silica (S
iO ₂ ) On a surface of a soda glass transparent substrate on which a film is formed, a light-shielding layer is provided so as to partition a portion where a pixel pattern is to be formed, and the liquid composition is applied using a spin coater, and then 80 ° C. For 2 minutes to form a coating film having a thickness of 1.5 μm. Next, after the substrate was cooled, wavelengths of 365 nm, 405 nm and 436 nm were applied to the coating film using a high-pressure mercury lamp through a photomask.
It was exposed to ultraviolet light of 100 mJ / cm ² containing 1 m of light for 1 second. Thereafter, the substrate is immersed in a 0.1% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute to perform a developing treatment, washed with ultrapure water, air-dried, and dried on each side.
A pixel array in which a red pixel pattern having a size of 0 μm × 300 μm was formed. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 1 hour to cure the pixel pattern, thereby forming a color filter on which a red pixel pattern was formed. Voltage holding ratio, pollution degree, of the liquid crystal display element manufactured using the obtained color filter,
Table 1 shows the evaluation results of the display state after the burn-in and the energization. In addition, when the obtained color filter was observed with an optical microscope, no omission and no omission were observed in the pixel pattern, and no undissolved substance remained in a region where the pixel pattern was not formed on the substrate. When the cross section of the obtained pixel pattern was observed with a scanning electron microscope, no undercut was observed. Further, when the hardness of the obtained pixel pattern was measured by a pencil hardness measurement method, it was 3H or more, which was sufficient for a color filter.

Example 2 A color filter having a green pixel pattern was formed in the same manner as in Example 1 except that 120 parts by weight of CI Pigment Green 7 was used as the component (A). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter. In addition, when the obtained color filter was observed with an optical microscope, no omission and no omission were observed in the pixel pattern, and no undissolved substance remained in a region where the pixel pattern was not formed on the substrate. When the cross section of the obtained pixel pattern was observed with a scanning electron microscope, no undercut was observed. Further, when the hardness of the obtained pixel pattern was measured by a pencil hardness measurement method, it was 3H or more, which was sufficient for a color filter.

Example 3 CI Pigment Blue 15: 6 was added as a component (A) to 12
A color filter having a blue pixel pattern was formed in the same manner as in Example 1 except that 0 part by weight was used.
Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter. In addition, when the obtained color filter was observed with an optical microscope, no omission and no omission were observed in the pixel pattern, and no undissolved substance remained in a region where the pixel pattern was not formed on the substrate. When the cross section of the obtained pixel pattern was observed with a scanning electron microscope, no undercut was observed. Further, when the hardness of the obtained pixel pattern was measured by a pencil hardness measurement method, it was 3H or more,
It had sufficient hardness as a color filter.

Example 4 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that the compound represented by the formula (4) was used as the component (E). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Example 5 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that the compound represented by the formula (6) was used as the component (E). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Example 6 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that the compound represented by the formula (10) was used as the component (E). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Example 7 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that poly (3-vinyloxetane) was used as the component (E). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Example 8 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that ethylenediaminetetraacetic acid was used as the component (E). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Example 9 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that polyvinylamine was used as the component (E). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Example 10 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that a methacrylic acid / styrene / 2-methacryloyloxyethyl isocyanate copolymer was used as the component (E). Formed. The voltage holding ratio of a liquid crystal display element manufactured using the obtained color filter,
Table 1 shows the evaluation results of the degree of contamination, the burn-in, and the display state after energization.

Example 11 A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that citric acid was used as the component (E). Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Example 12 Except that 18-crown-6 was used as the component (E),
In the same manner as in Example 2, a color filter having a green pixel pattern was formed. Voltage holding ratio, pollution degree, of the liquid crystal display element manufactured using the obtained color filter,
Table 1 shows the evaluation results of the display state after the burn-in and the energization.

Example 13 Silica gel (Aerosil 200, trade name) as the component (E)
A color filter having a green pixel pattern was formed in the same manner as in Example 2 except that Nippon Aerosil Co., Ltd. was used. Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Embodiment 14 Green and blue pixel patterns are sequentially formed on the substrate on which a red pixel pattern is formed in the same manner as in the first embodiment, in the same manner as in the second and third embodiments. Thus, a color filter on which three-color pixel patterns were formed was formed. Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Comparative Example 1 A color filter having a red pixel pattern was formed in the same manner as in Example 1 except that the component (E) was not used. Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

Comparative Example 2 A color filter having a pixel pattern of three colors was formed in the same manner as in Example 14 except that the component (E) was not used. Table 1 shows the evaluation results of the voltage holding ratio, the degree of contamination, the burn-in, and the display state after energization of the liquid crystal display element manufactured using the obtained color filter.

[0105]

[Table 1]

[0106]

EFFECTS OF THE INVENTION The radiation-sensitive composition for a color filter of the present invention does not cause a reduction in voltage holding ratio, image sticking or poor alignment, and has an excellent display state after energization. A display element can be provided. In addition, the color filter formed using the radiation-sensitive composition for a color filter of the present invention does not cause any dropout / deletion or undercut of the pixel pattern, and the area where the pixel pattern is not formed on the substrate. No undissolved matter remains and has sufficient hardness.

Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) G03F 7/004 505 G03F 7/004 505 7/032 501 7/032 501 (72) Inventor Takeshi Watanabe Tsukiji, Chuo-ku, Tokyo F-term (reference) 2-11-0224 JSR Corporation 2H025 AA00 AA04 AA13 AB13 AC01 AC04 AD01 BC12 BC14 BC42 BC43 BC51 BC82 BJ00 CA00 CA02 CA14 CA28 CB06 CB07 CB25 CB43 CB45 CB52 CC08 CC11 CC12 CC45 DA12 DA15 DB03 EB30 FA12

Claims (2)

[Claims] 1. A pollution degree defined by the following formula [I], comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator. Is 0.15 or less, the radiation-sensitive composition for a color filter. Pollution degree = (X−Y) / X (I) (where X is the measurement temperature 60 of a liquid crystal display element in which a nematic liquid crystal is injected using a substrate having an ITO film formed on one surface of a glass substrate). ° C and a voltage holding ratio at a frame period of 500 milliseconds. Y is the same nematic type using a substrate on which a radiation-sensitive composition is applied on one side of a glass substrate, baked, and then an ITO film is formed. This is the voltage holding ratio at a measurement temperature of 60 ° C. and a frame period of 500 milliseconds of the liquid crystal display element into which liquid crystal is injected.) 2. (E) an epoxy group-containing compound, an oxetane ring-containing compound, an amino group-containing compound, an amino group-substituted carboxylic acid compound, an isocyanate group-containing compound, a crown ether compound, an organic chelating agent other than the above, polyvinyl alcohol, The radiation-sensitive composition for a color filter according to claim 1, further comprising at least one component selected from the group consisting of an organic compound composed of polyethylene glycol or polyimide and an inorganic compound composed of an extender, a filler, or polyphosphoric acid.