JP2003015288A - Radiation sensitive composition for use in color liquid crystal display and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive composition capable of forming a color filter having satisfactory adhesion to a plastics substrate even if such low temperature treatment as not to cause deformation or yellowing to the plastics substrate is adopted when the color filter is formed on the plastics substrate and to provide a color filter formed form the composition. SOLUTION: The radiation sensitive composition contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator and (E) a thermal polymerization initiator.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Color liquid crystal display devices are most widely used in flat panel displays, but in recent years, with the spread of OA devices such as portable personal computers and word processors, and mobile phones, display quality has been improved. In addition to the ever-increasing performance requirements, there is an increasing demand for weight reduction and manufacturing cost reduction of color liquid crystal display devices.
Therefore, as a substrate for forming a color filter, the glass used in the past has been replaced with the glass used in the past.
Attempts have been made to use plastic substrates, as disclosed in US Pat. But,
When a conventionally known radiation-sensitive composition for a color liquid crystal display device is used to form a color filter on a plastic substrate, the substrate may be deformed or yellowed, resulting in color reproducibility and product yield. There was a problem. Also,
When the processing temperature in the color filter forming step is lowered in order to avoid the deformation and yellowing of the plastic substrate, there arises a problem in the adhesion between the formed color filter and the substrate. As described above, the radiation-sensitive composition suitably used for forming the color filter on the plastic substrate has not been known yet.

[0003]

The present invention has been made in view of the above circumstances, and an object thereof is to prevent the plastic substrate from being deformed or yellowing when forming a color filter on the plastic substrate. It is an object of the present invention to provide a radiation-sensitive composition capable of forming a color filter having sufficient adhesion to a substrate even when low-temperature treatment is adopted, and a color filter formed from the radiation-sensitive composition.

[0004]

According to the present invention, the above-mentioned problems are (A) a colorant, (B) an alkali-soluble resin,
(C) Polyfunctional monomer (D) Photopolymerization initiator and (E)
This is achieved by a radiation-sensitive composition for a color filter, which contains a thermal polymerization initiator, and a color filter formed therefrom. Incidentally, "radiation" in the present invention, visible light, ultraviolet rays, far ultraviolet rays, electron beams,
It means one including X-rays.

The constituents of the composition of the present invention will be described in detail below. (A) Colorant The colorant in the present invention is not particularly limited in color tone and may be appropriately selected depending on the intended use of the color filter to be obtained, and may be a pigment, a dye or a natural pigment.
Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance, , Pigments, particularly preferably organic pigments and / or carbon black are used.

Examples of the organic pigment include, for example, color index (CI; The Society of Dyers and Coloris).
(published by ts), compounds classified as Pigment (specifically, compounds having the following color index (CI) numbers) can be mentioned. CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 15
0, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 15
5, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 18
0, CI Pigment Yellow 185, CI Pigment Yellow 190, CI Pigment Yellow 211;

CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI
Pigment Orange 43, CI Pigment Orange 4
6, 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, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI
Pigment Red 174, CI Pigment Red 17
5, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187,
CI Pigment Red 188, CI Pigment Red 1
90, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI
Pigment Red 208, CI Pigment Red 20
9, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243,
CI Pigment Red 245, CI Pigment Red 2
54, 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 Green 136, CI Pigment Green 210; CI Pigment Brown 23, CI
Pigment Brown 25; CI Pigment Black 1,
CI Pigment Black 7. These organic pigments can be used alone or in admixture 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 pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue and navy blue. , Chrome oxide green, cobalt green,
Examples include amber, titanium black, synthetic iron black, carbon black and the like. These inorganic pigments may be used alone or in admixture of two or more. When the radiation-sensitive composition for a color liquid crystal display device of the present invention is used for forming pixels, one or more organic pigments are preferably used as a colorant, and for forming a black matrix. If used, preferably two or more organic pigments and / or carbon blacks are used as colorants.

In the present invention, each of the above-mentioned pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the surface of the pigment particles include the polymers described in JP-A-8-259876, and various commercially available polymers or oligomers for dispersing pigments. Further, 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 surfactants. Examples of the surfactant, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene n-octyl phenyl ethers, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-nonyl phenyl ethers; polyethylene glycol dilaurate, polyethylene glycol distearate Polyethylene glycol diesters such as; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethyleneimine, etc., as well as KP (Shin-Etsu Chemical Co., Ltd.) and Polyflow (Kyoeisha) Chemical Co., Ltd.), F-Top (Tochem Products Co., Ltd.), Megafac (Dainippon Ink and Chemicals Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.),
Asahi Guard, Surflon (above, Asahi Glass Co., Ltd.),
Disperbyk (Big Chemie Japan Co., Ltd.
), Sols Perth (Zeneca Co., Ltd.), EFKA (Fuka Chemicals Co., Ltd.), Addisper (Ajinomoto Co., Inc.)
Manufactured) and the like. These surfactants are
They can be used alone or in combination of two or more. The amount of the surfactant used is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the colorant.

(B) Alkali-Soluble Resin The alkali-soluble resin in the present invention includes (A) a developer that acts as a binder for the colorant and is used in the development treatment step when producing a color filter, Particularly preferably, as long as it has solubility in an alkaline developer, it is not particularly limited, for example, a carboxyl group, a phenolic hydroxyl group,
A copolymer of a photopolymerizable unsaturated monomer having an acidic functional group such as sulfonic acid and another copolymerizable unsaturated monomer (hereinafter referred to as "copolymerizable unsaturated monomer"). Can be mentioned.

Examples of the photopolymerizable unsaturated monomer having a carboxyl group (hereinafter referred to as “carboxyl group-containing unsaturated monomer”) include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid. Unsaturated carboxylic acids such as cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or their anhydrides; Trivalent or higher unsaturated polycarboxylic acid or anhydride thereof; divalent or higher succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], etc. Mono [(meth) acryloyloxyalkyl] esters of polycarboxylic acids of
Examples thereof include ω-carboxypolycaprolactone mono (meth) acrylate and other polymer mono (meth) acrylates having a carboxyl group and a hydroxyl group at both ends.

Among these carboxyl group-containing unsaturated monomers, particularly (meth) acrylic acid and succinic acid mono [2]
-(Meth) acryloyloxyethyl] and the like are preferable. The unsaturated monomer containing a carboxyl group may be used alone or
A mixture of two or more species can be used.

Examples of the photopolymerizable unsaturated monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene and m-hydroxy. -Α-methylstyrene, p-hydroxy-α-methylstyrene, N-o-hydroxyphenylmaleimide,
Examples thereof include Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide. These photopolymerizable unsaturated monomers having a phenolic hydroxyl group can be used alone or in admixture of two or more. Examples of the photopolymerizable unsaturated monomer having a sulfonic acid group include isoprene sulfonic acid and p-styrene sulfonic acid. These photopolymerizable unsaturated monomers having a sulfonic acid group can be used alone or in admixture of two or more.

Next, as the copolymerizable unsaturated monomer, for example, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc. may be used as a mono ( Macromonomers having a (meth) acryloyl group (hereinafter, simply referred to as "macromonomers"): N-phenylmaleimide, N
-O-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-
m-methylphenyl maleimide, Np-methylphenyl maleimide, N-o-methoxyphenyl maleimide,
N- (substituted) arylmaleimides such as Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide, and N-substituted maleimides such as N-cyclohexylmaleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-
Methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Aromatic vinyl compounds; indene, 1-methylindene, and other indenes;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (Meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-
Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2 -Phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) Acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol (meth) acrylate, etc. Japanese carboxylic acid esters; 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, Three
-Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl (meth) acrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; carvone such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Acid vinyl esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; (meth) acrylonitrile, α-chloroacrylonitrile,
Vinyl cyanide compounds such as vinylidene cyanide; (meth) acrylamide, α-chloroacrylamide, N-
Unsaturated amides such as 2-hydroxyethyl (meth) acrylamide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene can be mentioned. These copolymerizable unsaturated monomers may be used alone or
A mixture of two or more species can be used.

Of the above-mentioned copolymerizable unsaturated monomers, macromonomers, N-substituted maleimides, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate are preferable. In addition, polystyrene macromonomers and polymethyl (meth) acrylate macromonomers are particularly preferable among the macromonomers, and N-phenylmaleimide and N-cyclohexylmaleimide are particularly preferable among the N-substituted maleimides.

The preferred alkali-soluble resin in the present invention is a copolymer of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer (hereinafter, simply referred to as "carboxyl group-containing copolymer"). Can be mentioned.
As the carboxyl group-containing copolymer, a carboxyl group-containing unsaturated monomer, polystyrene macromonomer, polymethyl (meth) acrylate macromonomer,
N-phenyl maleimide, N-cyclohexyl maleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth)
A monomer containing at least one selected from the group of acrylates, and optionally further containing at least one selected from the group of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. The copolymer of the mixture (hereinafter referred to as "carboxyl group-containing copolymer (I)") is preferable, and particularly,
A carboxyl group-containing unsaturated monomer component containing (meth) acrylic acid as an essential component and optionally further containing succinic acid mono [2- (meth) acryloyloxyethyl];
Polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide,
At least one selected from the group consisting of N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate, and optionally styrene, methyl (meth) acrylate, allyl ( A copolymer of a monomer mixture further containing at least one selected from the group consisting of (meth) acrylate and phenyl (meth) acrylate (hereinafter, referred to as "carboxyl group-containing copolymer (I
I) ”. ) Is preferred.

Specific examples of the carboxyl group-containing copolymer (I) include (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate /
Polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyl Roxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth)
Acrylate / styrene copolymer, (meth) acrylic acid / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid /
Monosuccinate [2- (meth) acryloyloxyethyl]
/ N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer, (meth) acrylic acid /
Monosuccinate [2- (meth) acryloyloxyethyl]
/ N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) Acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-
Hydroxyethyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / Phenyl (meth) acrylate 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 (meth) acrylate macromonomer copolymer, (meth) acrylic acid /
Examples thereof include N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5
˜50 wt%, preferably 10-40 wt%. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, while if it exceeds 50% by weight. However, the solubility in an alkali developing solution becomes excessive, and when developing with an alkali developing solution, the pixels tend to come off from the substrate or the surface of the pixel becomes rough.

The polystyrene-reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is preferably 3,000 to 300, 000, more preferably 5,000 to 100,000. In addition, the polystyrene-equivalent number average molecular weight (hereinafter,
It is called "Mn". ) Is preferably 3,000 to 60,
000, more preferably 5,000 to 25,000. By using such an alkali-soluble resin having a specific Mw or Mn, a radiation-sensitive composition having excellent developability can be obtained, whereby a pixel having a sharp pattern edge can be formed, and Residues, background stains, and film residues are less likely to occur on the unexposed portion of the substrate and the light-shielding layer during development. Further, the ratio of Mw and Mn of the alkali-soluble resin in the present invention (Mw /
Mn) is usually 1 to 5, preferably 1 to 4. In the present invention, the alkali-soluble resin may be used alone or
A mixture of two or more species can be used.

The amount of the alkali-soluble resin used in the present invention is usually 10 with respect to 100 parts by weight of the colorant (A).
˜1,000 parts by weight, preferably 20 to 500 parts by weight. In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, the alkali developability may decrease,
There is a risk of background stains and film residue on the unexposed area of the substrate or on the light-shielding layer. On the other hand, when the amount exceeds 1,000 parts by weight, the colorant concentration decreases relatively, so the desired color of the thin film is obtained. Achieving concentrations can be difficult.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds. Examples of polyfunctional monomers are 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 and trimethylol. Polyacrylate or polymethacrylate of trivalent or higher polyhydric alcohol such as propane, pentaerythritol, dipentaerythritol and their dicarboxylic acid modified products; polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin, etc. Oligoacrylates or oligomethacrylates;
Diacrylates or dimethacrylates of hydroxyl-terminated polymers such as hydroxypoly-1,3-butadiene at both ends, hydroxypolyisoprene at both ends, and hydroxypolycaprolactone at both ends, and tris (2-acryloyloxyethyl) phosphate , Tris (2-methacryloyloxyethyl) phosphate and the like.

Of these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products are preferable,
Specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol pentamethacrylate. Pentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate are preferable, and particularly trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate have high pixel strength, excellent pixel surface smoothness, and unexposed areas. Dirt, film residue, etc. are generated on the substrate and the light shielding layer of Hard in terms preferred. These polyfunctional monomers may be used alone or in admixture of two or more.

The amount of the polyfunctional monomer used in the present invention is (B) 100 parts by weight of the alkali-soluble resin,
Usually, it is 5 to 500 parts by weight, preferably 20 to 300 parts by weight. In this case, when the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be lowered, while when it exceeds 500 parts by weight, for example, the alkali developability is lowered. However, there is a tendency that scumming, film residue and the like are likely to occur on the substrate of the unexposed portion or the light shielding layer.

In the present invention, a part of the polyfunctional monomer may be replaced with a monofunctional monomer having one polymerizable unsaturated bond. Examples of the monofunctional monomer include a carboxyl group-containing unsaturated monomer, a copolymerizable unsaturated monomer, N-vinyl succinimide, and N-vinyl, which are exemplified for the (B) alkali-soluble resin. Pyrrolidone, N-vinylphthalimide, N-vinyl-2-
Piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinylindole, N-vinylindoline, N-vinylbenzimidazole, N -Vinylcarbazole, N-vinylpiperidine, N-vinylpiperazine, N-vinylmorpholine,
N-vinyl derivatives such as N-vinylphenoxazine; N
In addition to-(meth) acryloylmorpholine, commercially available products include M-5300, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.). These monofunctional monomers may be used alone or in admixture of two or more. The use ratio of the monofunctional monomer is based on the total of the polyfunctional monomer and the monofunctional monomer,
Usually, it is 90% by weight or less, preferably 50% by weight or less. In this case, the proportion of monofunctional monomer used is 90% by weight.
When it exceeds, the strength and surface smoothness of the pixels and the black matrix tend to decrease.

(D) Photopolymerization Initiator The photopolymerization initiator in the present invention is irradiated with radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays (hereinafter, referred to as “exposure”) to obtain the above (). C) Compounds capable of generating active species capable of initiating the polymerization of polyfunctional monomers and optionally monofunctional monomers. Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α
-Diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds and the like can be mentioned. In the present invention, the photopolymerization initiator can be used alone or as a mixture of two or more kinds, and as the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound and a triazine compound can be used. At least one selected from the group is preferable.

The general amount of the photopolymerization initiator used in the present invention is usually 0.01 to 100 parts by weight based on 100 parts by weight of the (C) polyfunctional monomer and the monofunctional monomer. It is 80 parts by weight, preferably 1 to 60 parts by weight. In this case, if the amount of the photopolymerization initiator used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the 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-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one and the like can be mentioned.

Of these acetophenone compounds,
Particularly, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 are preferable. The acetophenone compounds may be used alone or in combination of two or more.

In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is (C).
It is 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.
-60 parts by weight, more preferably 1-30 parts by weight. In this case, the amount of the acetophenone 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 color filter in which the colored layer pattern is arranged according to a predetermined arrangement.
If it exceeds 0 part by weight, the formed colored layer tends 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-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,
2,2'-bis (2,4,6-tribromophenyl)-
4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, more preferable 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, particularly preferred compound is 2,2′-
Bis (2,4-dichlorophenyl) -4,4 ', 5
It is 5'-tetraphenyl-1,2'-biimidazole.

These biimidazole compounds are excellent in solubility in a solvent, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and allow a curing reaction to sufficiently proceed by exposure with a small amount of energy. At the same time, since the contrast is high and the curing reaction does not occur in the unexposed area, the exposed coating film is a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer. It is possible to form a high-definition color filter in which pixel patterns without undercut are arranged according to a predetermined arrangement. The biimidazole compounds may be used alone or in admixture of two or more.

In the present invention, the amount of the biimidazole compound used as the photopolymerization initiator is (C).
It is 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.
-30 parts by weight, more preferably 1-20 parts by weight. In this case, the amount of the biimidazole 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 color filter in which the colored layer pattern is arranged according to a predetermined arrangement.
If the amount exceeds 0 parts by weight, the formed colored layer tends to come off from the substrate or the surface of the pixel may be roughened during development.

-Hydrogen Donor- In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use the following hydrogen donor in combination because the sensitivity can be further improved. The "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure.

As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable. The mercaptan-based compound has a benzene ring or a heterocycle as a nucleus, and has one or more, preferably 1 to 3, more preferably 1 to 2 mercapto groups directly bonded to the nucleus (hereinafter, referred to as ""Mercaptan-based hydrogen donor"). The amine compound has a benzene ring or a heterocycle as a nucleus, and has at least one amino group directly bonded to the nucleus, preferably 1 to 3,
More preferably, it comprises a compound having 1 or 2 (hereinafter referred to as "amine-based hydrogen donor"). In addition, these hydrogen donors can also 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, respectively, and can have both a benzene ring and a heterocycle. When two or more of these rings are contained, a condensed ring is required. It may or may not be formed. When the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups are substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. In addition, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded through a divalent organic group such as an alkylene group or two sulfur atoms are combined. It may have structural units attached in the form of disulfides. Furthermore, the mercaptan-based hydrogen donor has a carboxyl group, an alkoxycarbonyl group,
It may be substituted with a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such a mercaptan hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzothiazole.
Examples thereof include mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-2,5-dimethylaminopyridine. Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable,
2-Mercaptobenzothiazole is particularly preferable.

Further, the amine-based hydrogen donor may have one or more benzene rings or one or more heterocycles,
It can also have both a benzene ring and a heterocycle,
When it has two or more of these rings, it may or may not form a condensed ring. In the amine-based hydrogen donor, one or more amino groups may be substituted with an alkyl group or a substituted alkyl group, and at a position other than the amino group, a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone and 4-dimethylaminoproton. Piophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like can be mentioned. Among these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4 ′ is particularly preferable.
-Bis (diethylamino) benzophenone is preferred.
The amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than the biimidazole-based compound.

In the present invention, the hydrogen donors may be used alone or in admixture of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors may be used. It is preferable to use it in combination because the formed colored layer is less likely to fall off the substrate during development, and the strength and sensitivity of the colored layer 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, 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4 , 4′-bis (diethylamino) benzophenone and the like, and a more preferable 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-based hydrogen donor and the amine-based hydrogen donor in the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor is usually 1:
It is 1 to 1: 4, preferably 1: 1 to 1: 3.

In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. It is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 parts by weight, the effect of improving the sensitivity tends to decrease, while if it exceeds 40 parts by weight, the formed colored layer falls off from the substrate during development. Tends to be easier.

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)
Examples of triazine-based compounds having a halomethyl group such as -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. be able to.

Of these triazine compounds, 2-
[2- (3,4-dimethoxyphenyl) ethenyl]-
4,6-bis (trichloromethyl) -s-triazine and the like are preferable. The triazine compounds may be used alone or in admixture of two or more.

In the present invention, when the triazine compound is used as the photopolymerization initiator, the amount used is 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. It is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, the amount of the triazine compound used is 0.0
If it is less than 1 part by weight, curing by exposure becomes insufficient and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, it is formed. The colored layer tends to fall off the substrate during development.

(E) Thermal Polymerization Initiator The (E) thermal polymerization initiator in the present invention is an initiator that generates radicals by heat treatment when forming a color filter, and includes (C) the polyfunctional initiator and It is a compound capable of generating an active species capable of initiating the polymerization of a monofunctional monomer optionally used. Examples of such thermal polymerization initiators include azo compounds, organic peroxides and hydrogen peroxide. Of these, azo compounds are preferably used. As the azo compound,
2,2'-azobisisobutyronitrile, 2,2'-azobis (2-
Methyl butyronitrile), 1,1'-azobis (cyclohexene-1-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methyl Ethyl) azo]
Formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2 '
-Azobis [N- (2-propenyl) -2-methylpropionamide], 2,2'-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl -2-Methylpropionamide], 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (dimethyl-2-methylpropionamide), 2,2'-azobis (dimethyl -2-methylpropionate), 2,2'-azobis (2,4,4-trimethylpentene), and the like. Among these, 2,2'-azobisisobutyronitrile, 2 , 2'-azobis
(2,4-dimethylvaleronitrile) and the like are preferable.

Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1'-bis- (t-butylperoxy) cyclohexane. Among them, Lauroyl peroxide and the like are preferable.
(E) When an organic peroxide or hydrogen peroxide is used as the thermal polymerization initiator, these may be used together with a reducing agent to prepare a redox type initiator.

The amount of the (E) thermal polymerization initiator used is 0.1 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the (C) polyfunctional monomer. With a usage amount within this range, a color filter having good adhesion to the substrate can be provided even by heat treatment at a low temperature at which the plastic substrate is not deformed or yellowed, and does not cause burn-in when used as a liquid crystal display device. Giving the composition.

Other Additives The radiation-sensitive composition for a color liquid crystal display device of the present invention contains the above components (A) to (E), but may contain other additives as required. You can also Examples of such additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers and poly (fluoroalkyl acrylates); nonionic surfactants,
Surfactants such as cationic surfactants and anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) -3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Adhesion promoters such as 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6)
-T-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-
Examples thereof include UV absorbers such as methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; and aggregation inhibitors such as sodium polyacrylate.

Solvent The radiation-sensitive composition for a color liquid crystal display device of the present invention contains the above components (A) to (E) and optionally other additives, but is preferably a solvent. To prepare a liquid composition. As the solvent, as long as it is a solvent which disperses or dissolves the components (A) to (E) and the additive component constituting the radiation-sensitive composition, 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, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol Roh -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

(Poly) alkylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; methyl ethyl ketone,
Ketones such as cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, 2-
Lactic acid alkyl esters such as ethyl hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate,
Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, N-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, Butyric acid n
-Butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, other esters such as ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N-dimethylformamide, N, N-
Examples thereof include amides such as 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-methyl-3-methoxy Butyl propionate, n-butyl acetate, i-butyl acetate,
N-Pentyl formate, i-pentyl acetate, n-propionate
-Butyl, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferable. The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the above solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone,
Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate. It is also possible to use a high boiling point solvent such as The high boiling point solvents may be used alone or in admixture of two or more.

The amount of the solvent used is not particularly limited, but from the viewpoint of coating property, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is , Preferably 5 to 50% by weight, particularly preferably 1
The amount is preferably 0 to 40% by weight.

Method for Forming Color Filter Next, a method for forming a color filter using the radiation-sensitive composition for color filter of the present invention will be described. First, a liquid composition of a radiation-sensitive composition in which, for example, a red pigment is dispersed is applied on the surface of a substrate on which a light-shielding layer has been formed so as to partition a portion for forming pixels, if necessary, and then prebaked. Is carried out to evaporate the solvent and form a coating film. Next, this coating film is exposed to radiation through a photomask, then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film, and then post-baked to form a red pixel pattern. A color filter arranged in a predetermined array is formed. Then, using a liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, in the same manner as above, by sequentially forming a green color filter and a blue color filter on the same substrate, A color filter in which colored layers of three primary colors of red, green and blue are arranged on a substrate is obtained. Here, the formation order of the color filters of each color is not limited to the above.

Examples of the substrate used for forming the color filter include glass, which is generally used, and plastic substrates such as polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyether sulfone, and polyester. be able to. For these substrates, if desired, chemical treatment with a silane coupling agent, plasma treatment, ion plating,
Appropriate pretreatments such as sputtering, a vapor phase reaction method, and vacuum deposition can be performed. When applying the liquid composition of the radiation-sensitive composition to the substrate, spin coating, cast coating,
An appropriate coating method such as roll coating can be adopted.
The coating thickness is usually 0.1 to 10 after removal of the solvent.
The thickness is 10 μm, preferably 0.2 to 5.0 μm, and particularly preferably 0.2 to 3.0 μm.

The conditions of the prebaking are such that, when a clean oven is used, the heating temperature is usually 60 to 110 ° C, preferably 60 to 80 ° C, and the heating time is usually 2 to 15 ° C.
Minutes, preferably 2 to 10 minutes. As the radiation used when forming the color filter, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable. . The irradiation energy amount of radiation is usually 1
To 1000 mJ / cm ² , preferably 30 to 300 mJ
/ Cm ² . Further, as the alkaline developer,
For example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0]
-7-undecene, 1,5-diazabicyclo- [4.
An aqueous solution of 3.0] -5-nonene or the like is preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline developer. After the alkali development, it is usually washed with water. As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid pour) developing method and the like can be applied, and the developing condition is preferably 5 to 300 seconds at room temperature.

The conditions of the post-baking are usually 100 to 250 ° C., preferably 100 to 230 ° C. as a heating temperature.
However, the radiation-sensitive composition of the present invention, especially when used for forming a color filter on a plastic substrate, has a heating temperature of 100 to
A temperature range of 150 ° C., and further 100 to 120 ° C. can be adopted, whereby deformation and yellowing of the plastic used as the substrate can be avoided. The heating time is usually 20 minutes to 1 hour, preferably 30 minutes to 1 hour.
The color filter thus formed is, for example,
It is extremely useful for transmissive or reflective color liquid crystal display devices, color image pickup tube elements, color sensors and the like.

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

EXAMPLES Example 1 (A) CI Pigment Red 177 and CI as colorants
Pigment Red 224, 65/35 (weight ratio) mixture 100 parts by weight, (B) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer as an alkali-soluble resin (copolymerization weight ratio = 15 / 25/35/10/1
5, Mw = 30,000, Mn = 10,000) 70 parts by weight, (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-benzyl-2 as a photopolymerization initiator -Dimethylamino-1- (4
-Morpholinophenyl) butanone-1 50 parts by weight,
(E) A liquid composition of a radiation-sensitive composition by mixing 2 parts by weight of N, N'-azoisobutyronitrile as a thermal polymerization initiator and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. (R1) was prepared. <Formation and Evaluation of Color Filter> Liquid composition (R
1) was applied onto the surface of a polystyrene sulfonic acid substrate using a spin coater, and then prebaked in a clean oven at 90 ° C. for 10 minutes to give a film thickness of 1.7 μm.
m coating film was formed. Then, after cooling this substrate to room temperature, the coating film was exposed to ultraviolet rays containing wavelengths of 365 nm, 405 nm and 436 nm at an exposure amount of 100 mJ / cm ² through a photomask using a high pressure mercury lamp. Then, this substrate is immersed in a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute to develop it,
The glass substrate was rubbed with a soft sponge to remove the colored resin layer other than the pixel pattern. Then, wash with ultrapure water, air dry, and then in a clean oven at 150 ° C for 3
Post-baking was performed for 0 minutes to form a red stripe-shaped color filter on the substrate. When the obtained striped color filter was observed with an optical microscope, no development residue was found on the unexposed area of the substrate. Then, 1 mm with a cutter on the obtained stripe
The tape peeling test was performed in accordance with JIS K5400 8.5 by making cuts in a grid pattern with 10 columns and 10 rows. As a result, 100 grids on the pixel obtained by using (R1) were not peeled at all.

Comparative Example 1 (E) A liquid composition (R2) was prepared in the same manner as in Example 1 except that the thermal polymerization initiator was not added. <Formation and Evaluation of Color Filter> Liquid composition (R
Except that the liquid composition (R2) was used instead of 1),
In the same manner as in Example 1, a red stripe stripe color filter was formed on the substrate and evaluated.
When the obtained striped color filter was observed with an optical microscope, no development residue was found on the unexposed area of the substrate. However, when a tape peeling test was performed in the same manner as in Example 1, 40 of 100 grids on the pixel obtained by using (R2) were peeled off.

Example 2 (A) CI Pigment Blue 15: 6 and C.I.
95/5 with I. Pigment Violet 23 (weight ratio)
55 parts by weight of the mixture, (B) a methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer as an alkali-soluble resin (copolymerization weight ratio = 15 /
15/70, Mw = 25,000, Mn = 10,000
0) 75 parts by weight, (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D)
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' as a photopolymerization initiator
6 parts by weight of biimidazole, 6 parts by weight of 4,4′-bis (diethylamino) benzopheno as an amine-based hydrogen donor, 3 parts by weight of 2-mercaptobenzothiazole as a mercaptan-based hydrogen donor, and (E) as a thermal polymerization initiator N,
A liquid composition (B1) of a radiation-sensitive composition was prepared by mixing 2 parts by weight of N'-azoisobutyronitrile and 700 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 300 parts by weight of cyclohexanone. <Formation and Evaluation of Color Filter> Liquid composition (R
Except that the liquid composition (B1) was used instead of 1),
In the same manner as in Example 1, a blue stripe color filter was formed on the substrate and evaluated. When the obtained striped color filter was observed with an optical microscope, no development residue was found on the unexposed area of the substrate. Further, it was judged by the tape peeling test that the adhesion of the obtained pixel to the substrate was excellent.

Example 3 (A) CI Pigment Green 36 and CI as colorants
Pigment Yellow 150: 65/35 (weight ratio) mixture 100 parts by weight, (B) Alkali-soluble resin: methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15 /
15/70, Mw = 25,000, Mn = 10,000
0) 75 parts by weight, (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D)
10 parts by weight of a triazine compound (3) as a photopolymerization initiator, (E) 2 parts by weight of N, N'-azoisobutyronitrile as a thermal polymerization initiator, and 700 parts by weight of propylene glycol monomethyl ether acetate as a solvent. A liquid composition (G1) of the radiation-sensitive composition was prepared by mixing 300 parts by weight of cyclohexanone. <Formation and Evaluation of Color Filter> Liquid composition (R
Except that the liquid composition (G1) was used instead of 1),
In the same manner as in Example 1, a green striped color filter was formed on the substrate and evaluated. When the obtained striped color filter was observed with an optical microscope, no development residue was found on the unexposed area of the substrate. Further, it was judged by the tape peeling test that the adhesion of the obtained pixel to the substrate was excellent.

[0066]

According to the present invention, when a color filter is formed on a plastic substrate, a color filter having sufficient adhesion to the substrate even when a low-temperature treatment that does not deform or yellow the plastic substrate is adopted. It is possible to obtain a radiation-sensitive composition capable of forming a film, and a color filter formed from the composition.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H025 AA14 AB13 AC01 AD01 BC13                       BC42 BC53 BC84 CA00 CA18                       CA23 CB42 CC11 FA17 FA29                 2H048 BA45 BA48 BB42                 2H091 FA02Y FB04 GA01 LA30

Claims (5)

[Claims] 1. A colorant containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator and (E) a thermal polymerization initiator. A radiation-sensitive composition for a color liquid crystal display device. 2. The (E) thermal polymerization initiator is an azo compound,
The radiation-sensitive composition for a color liquid crystal display device according to claim 1, comprising at least one selected from the group consisting of organic peroxides and hydrogen peroxide. 3. The (B) alkali-soluble resin comprises (a) at least one photopolymerizable unsaturated monomer having at least one carboxyl group, and (b) a mono (meth) at the end of the polymer molecular chain. The macromonomers having an acryloyl group, N-position-substituted maleimides, 2-hydroxy (meth) acrylate, and a copolymer with at least one kind selected from the group of benzyl (meth) acrylate are included in claim 1 or 2. The radiation-sensitive composition for color liquid crystal display device of. 4. The color liquid crystal display device according to claim 1, wherein the radiation-sensitive composition for color liquid crystal display device is for forming a color filter on a plastic substrate. Radiation-sensitive composition. 5. A color filter formed from the radiation-sensitive composition for a color liquid crystal display device according to claim 1.