JP2004212944A - Radiation-sensitive composition for color filter, color filter, color liquid crystal display device, and method for forming colored layer for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition for a color filter and a color filter for a color filter, which can form a colored layer having a uniform film thickness with high product yield and high efficiency without causing application unevenness during application by a slit die coater. A method for forming a layer is provided.
The radiation-sensitive composition for a color filter contains (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photoradical generator, and (E) a solvent. When the viscosity is A (mPa · s), the surface tension is B (mN / m), and the coating speed is V (m / s), the value of (A × V ÷ B) is 4 It is characterized by being less than 0.0 × 10 ^-2 , and is used for coating with a slit die coater.
The method for forming a colored layer for a color filter is characterized in that the composition is used and the coating speed is 0.07 m / s or more and 0.15 m / s or less.
[Selection diagram] None

Description

  The present invention relates to a radiation-sensitive composition for a color filter, a color filter, a color liquid crystal display device, and a method for forming a color layer for a color filter. More specifically, the present invention relates to a transmission type or reflection type color liquid crystal display device, and a color image pickup tube. Useful for the production of color filters used in devices and the like, radiation-sensitive composition for color filters used for coating with a slit die coater, color having a colored layer formed from the radiation-sensitive composition for color filters The present invention relates to a filter, a color liquid crystal display device including the color filter, and a method for forming a color filter colored layer using the color filter radiation-sensitive composition.

  In producing a color filter using a colored radiation-sensitive composition, application by a spin coater or a slit / spin coater is generally performed, but in recent years, a coating liquid is applied with high efficiency to reduce costs. For the purpose, a coating machine without a spin mechanism, that is, a slit die coater has been attracting attention.

  In recent years, in order to increase the number of chamfers on one substrate, the size of the substrate has been increasing, and therefore, it is necessary to increase the coating speed and prevent the tact time from becoming excessive. .

  This slit die coater is provided with a slit die having a slit nozzle directed in the coating direction as introduced in Non-Patent Document 1 and Non-Patent Document 2, for example. This is a device that discharges the coating liquid from the slit nozzle while moving in the coating direction, and can apply the coating liquid to the substrate without waste, compared to a rotary coating machine such as a spinner. The tact time is short and energy consumption can be saved.

However, if the coating speed is increased when coating with a slit die coater, the conventional radiation-sensitive composition for a color filter loses the balance between the discharge speed from the slit nozzle and the wettability to the substrate, resulting in uneven coating. There was a problem that occurred.
Monthly Display (published by Techno Times Co., Ltd.), '02 September issue, P.111-115 Monthly Display (published by Techno Times Co., Ltd.), '02 November issue, P.36-41

  SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive composition for a color filter and a color filter, which can form a uniform colored layer with high product yield and high efficiency without causing application unevenness when coating with a slit die coater. It is an object of the present invention to provide a method for forming a colored layer for use. Still other objects and advantages of the present invention will become apparent from the following description.

  The present inventors have conducted intensive studies on the above-mentioned problems relating to the slit die coater. As a result, the specific parameters determined from the viscosity and surface tension of the radiation-sensitive composition used for forming the color filter and the coating speed were applied. The inventors have found that there is a close relationship with the workability, and have accomplished the present invention.

According to the present invention, the above objects and advantages of the present invention are:
In a radiation-sensitive composition containing (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photoradical generator, and (E) a solvent, the viscosity is defined as A (mPa S), when the surface tension is B (mN / m) and the coating speed for forming the colored layer is V (m / s), the value obtained by the formula (A × V ÷ B) Is less than 4.0 × 10 ^-2, which is achieved by a radiation-sensitive composition for a color filter used for coating with a slit die coater.

  The term “radiation” as used in the present invention means those including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

According to the present invention, the problem is, secondly,
A method for forming a colored layer on a substrate using the radiation-sensitive composition for a color filter, wherein a coating speed of the radiation-sensitive composition is 0.07 m / s or more. Method for forming a color layer for a color filter by a slit die coater,
Achieved by

  ADVANTAGE OF THE INVENTION According to this invention, the coating nonuniformity does not generate | occur | produce at the time of application | coating by a slit die coater, and the coloring layer for color filters of a uniform film thickness can be formed with high product yield and high efficiency.

  Therefore, the radiation-sensitive composition for a color filter and the method for forming a color layer for a color filter of the present invention are extremely suitably used for forming various color filters including a color filter for a color liquid crystal display device in the field of electronics. can do.

  Hereinafter, the present invention will be described in detail.

Radiation-sensitive composition for color filter- (A) pigment-
As the pigment in the present invention, an organic pigment is preferable because a color filter is required to have high purity and high transmittance coloration and heat resistance.

As the organic pigment, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colorists), specifically, a color index (CI) number as shown below is attached. Can be mentioned.
CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 211;
CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 71;
CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254;
CI Pigment Violet 19, Pigment Violet 23, Pigment Violet 29;
CI Pigment Blue 15, CI Pigment Blue 60, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6,
CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 136, CI Pigment Green 210;
CI Pigment Brown 23, CI Pigment Brown 25;
These organic pigments can be used alone or in combination of two or more.

  In the present invention, the organic pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

  Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, 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.

  Further, in the present invention, one or more dyes and natural pigments may be used in combination with the pigment, as the case requires.

In the present invention, the pigment can be used by modifying its particle surface with a polymer, if desired. Examples of the polymer for modifying the particle surface of the pigment include a polymer described in Patent Document 1 and various commercially available polymers or oligomers for dispersing a pigment.
JP-A-8-259876

  In the present invention, the pigment can be used together with a dispersant, if desired.

  Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, 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, 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; KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products Co., Ltd.), Megaf (Manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo 3M Limited), Asahiguard, Surflon (manufactured by Asahi Glass Co., Ltd.), Disperbyk (manufactured by Big Chemie Japan KK), Solsperse (Manufactured by Seneca Corporation).

  These surfactants can be used alone or in combination of two or more.

  The amount of the dispersant used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the pigment.

-(B) Alkali-soluble resin-
As the alkali-soluble resin in the present invention, (A) a developer which acts as a binder for the pigment and which is used in a developing step of producing a color filter, particularly preferably a soluble in an alkali developer It has. Although not particularly limited, an alkali-soluble resin having a carboxyl group is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, referred to as “carboxyl group-containing unsaturated monomer”) ) And another copolymerizable ethylenically unsaturated monomer (hereinafter, referred to as “copolymerizable unsaturated monomer”) (hereinafter, referred to as “carboxyl group-containing copolymer”). Is preferred.

Examples of carboxyl group-containing unsaturated monomers include:
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, 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, mesaconic acid and anhydrides thereof;
Trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof;
Mono [(meth) acryloyloxyalkyl] of divalent or higher polycarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate Esters;
Examples thereof include polymer mono (meth) acrylates having a carboxy group and a hydroxyl group at both terminals, such as ω-carboxypolycaprolactone mono (meth) acrylate.

  Of these carboxyl group-containing unsaturated monomers, mono (2-acryloyloxyethyl) succinate and mono (2-acryloyloxyethyl) phthalate are M-5300 and M-5400 (Toagosei Co., Ltd., respectively). Co., Ltd.).

  The unsaturated monomers containing a carboxyl group may be used alone or in combination of two or more.

Further, as the copolymerizable unsaturated monomer, for example,
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m Aromatic vinyl compounds such as -vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;

Indenes such as indene and 1-methylindene;
(Meth) methyl 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 Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, etc. Saturated carboxylic esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; vinyl carboxylic acid 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 (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;
Macromonomers having a mono (meth) acryloyl group at the terminal of a polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane, can be mentioned.

  These copolymerizable unsaturated monomers can be used alone or in combination of two or more.

  As the carboxyl group-containing copolymer in the present invention, (meth) acrylic acid is an essential component, and in some cases, mono [2- (meth) acryloyloxyethyl] succinate and ω-carboxypolycaprolactone mono (meth) acrylate And a carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group consisting of styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, and benzyl ( A copolymer with at least one selected from the group consisting of (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer is preferable.

Specific examples of such a copolymer include:
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer 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 copolymer,
Methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monosuccinic acid [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 / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer Coalescing,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In this case, if the copolymerization ratio is less than 5% by weight, the solubility of the obtained radiation-sensitive composition in an alkali developer tends to decrease, while if it exceeds 50% by weight, the solubility in an alkali developer becomes poor. When developed with an alkali developer, the coloring layer tends to drop off from the substrate and the pixel surface tends to be rough.

  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) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000.

  Further, the number average molecular weight in terms of polystyrene (hereinafter, referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin is preferably from 1,000 to 40,000. Preferably it is 2,000-20,000.

  The ratio (Mw / Mn) of Mw to Mn of the alkali-soluble resin is preferably 1 to 5, more preferably 1 to 4.

  In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition excellent in developability is obtained, whereby a pixel pattern having a sharp pattern edge can be formed. In addition to the formation, residue, background stain, film residue, and the like hardly occur on the unexposed portion of the substrate and the light shielding layer during development.

  In the present invention, the alkali-soluble resin (B) can be used alone or in combination of two or more.

The amount of the (B) alkali-soluble resin used in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight, based on 100 parts by weight of the (A) pigment. In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, alkali developability may be reduced, or background contamination or a film residue may be generated on a substrate or a light shielding layer in an unexposed portion. If the amount exceeds 1,000 parts by weight, the pigment concentration is relatively reduced, so that it may be difficult to achieve a target color density as a thin film.
-(C) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.

Examples of such polyfunctional monomers include, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol, and dicarboxylic acid-modified products thereof;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spirane resin;
Di (meth) acrylates of hydroxyl-terminated polymers such as hydroxyl-terminated hydroxy poly-1,3-butadiene, hydroxyl-terminated polyisoprene, hydroxyl-terminated hydroxypolycaprolactone;
Tris [2- (meth) acryloyloxyethyl] phosphate and the like can be mentioned.

  Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and modified products of dicarboxylic acids, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Preferred are meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, particularly trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Acrylate is preferred because it has excellent strength and surface smoothness of the colored layer, and hardly causes background stain, film residue, and the like on the unexposed portion of the substrate and the light-shielding layer.

  The polyfunctional monomers may be used alone or in combination of two or more.

  The amount of the polyfunctional monomer used in the present invention is preferably 50 to 200 parts by weight, more preferably 75 to 150 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B). In this case, if the amount of the polyfunctional monomer used is less than 50 parts by weight, the strength and surface smoothness of the colored layer tend to decrease, while if it exceeds 200 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 having one polymerizable unsaturated bond.

  Examples of the monofunctional monomer include, for example, the same monomers as the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for the alkali-soluble resin (B), and N- (meta- ) Acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and as commercial products, M-5300, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like. Can be.

  These monofunctional monomers can be used alone or in combination of two or more.

  The proportion of the monofunctional monomer used is preferably 50% by weight or less, more preferably 20% by weight or less, based on the total amount of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 50% by weight, the strength and the surface smoothness of the colored layer may be insufficient.

  In the present invention, the total amount of the polyfunctional monomer and the monofunctional monomer is preferably 50 to 300 parts by weight, more preferably 75 to 100 parts by weight of (B) the alkali-soluble resin. １８０180 parts by weight. In this case, if the total amount is less than 50 parts by weight, the strength and surface smoothness of the colored layer tend to decrease, while if it exceeds 300 parts by weight, for example, alkali developability decreases or unexposed parts In some cases, background dirt, film residue, and the like easily occur on the substrate or the light-shielding layer.

-(D) Photo-radical generator-
The photo-radical generator in the present invention is obtained by exposing the (C) polyfunctional monomer and optionally a monofunctional monomer by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. A compound capable of generating a radical capable of initiating polymerization.

  Such photo-radical generators 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 photoradical generator may be used alone or as a mixture of two or more kinds. Examples of the photoradical generator in the present invention include acetophenone-based compounds, biimidazole-based compounds and triazine-based compounds. At least one member selected from the group is preferable.

  Among the preferred photoradical generators in the present invention, specific examples of acetophenone-based compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- (4-methylthiophenyl)-. 2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane -1-one and the like.

  Among these acetophenone-based compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone -1 and the like are preferable.

  The acetophenone-based compounds can be used alone or in combination of two or more.

  In the present invention, when the acetophenone-based compound is used as the photoradical generator, the amount used is 5 to 80 parts by weight based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. Parts by weight, more preferably 10 to 60 parts by weight, even more preferably 20 to 50 parts by weight. In this case, if the amount of the acetophenone-based compound is less than 5 parts 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 the portion, the formed colored layer tends to fall off the substrate during development.

Further, 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.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 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 the like are more preferred, and in particular, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2. '-Bimidazole is preferred.

  The biimidazole-based compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, and has high sensitivity. Since the curing reaction does not occur in the part, the exposed coating film is clearly divided into a cured part insoluble in the developer and an uncured part having a high solubility in the developer. Accordingly, 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-based compound is used as the photoradical generator, the amount used is preferably based on 100 parts by weight of the total of the polyfunctional monomer (C) and the monofunctional monomer. 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, still more preferably 0.1 to 20 parts by weight. In this case, if the amount of the biimidazole-based compound used is less than 0.1 part by weight, curing by exposure may be 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 40 parts by weight, the formed colored layer tends to fall off the substrate during development.
-Hydrogen donor-
In the present invention, when a biimidazole-based compound is used as the photoradical generator, 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 present invention, a mercaptan compound, an amine compound and the like 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 ”).

  Further, the amine 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 amino groups directly bonded to the mother nucleus (hereinafter, referred to as a compound). , "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 heterocycles, and can have both benzene rings and heterocycles. 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 is substituted with an alkyl, aralkyl, or aryl group as long as at least one free mercapto group remains. As long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms It may have structural units linked in the form of disulfides.

  Further, the mercaptan-based hydrogen donor may be substituted at a site other than the mercapto group with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like.

  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 can be mentioned.

  Among these mercaptan hydrogen donors, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and the like 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, or can have both a benzene ring and a heterocycle, and when it has two or more of these rings, A condensed ring may or may not be formed.

  In the amine hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy It may be substituted by a carbonyl 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, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, and 4-dimethylaminobenzonitrile.

  Among these amine hydrogen donors, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and the like are preferable, and 4,4'-bis (diethylamino) benzophenone is particularly preferable.

  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 can be used alone or as a mixture of two or more. However, the hydrogen donors may be used in combination with one or more mercaptan hydrogen donors and one or more amine hydrogen donors. This is preferred because the formed colored layer hardly falls 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 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, etc., and a particularly preferred combination is 2-mercaptobenzothione. Is a tetrazole / 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 of the hydrogen donor is preferably 0 to 100 parts by weight of the total of the polyfunctional monomer (C) and the monofunctional monomer. 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight. In this case, if the amount of the hydrogen donor is less than 0.1 part by weight, the effect of improving sensitivity tends to decrease, while if it exceeds 30 parts by weight, the formed colored layer falls off the substrate during development. Tend to be easier.

  Specific examples of the triazine-based 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 (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-E Triazine-based compounds having a halomethyl group such as (xystyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferred.

  The triazine compounds can be used alone or in combination of two or more.

  In the present invention, when a triazine-based compound is used as a photoradical generator, the amount used is preferably 1 part by weight based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. The amount is from 40 to 40 parts by weight, more preferably from 1 to 30 parts by weight, particularly preferably from 1 to 20 parts by weight. In this case, if the amount of the triazine-based compound is less than 1 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 colored layer tends to fall off the substrate during development.

-Additive-
The radiation-sensitive composition for a color filter of the present invention may contain various additives as necessary.

  As the additive, an organic acid or an organic amino compound (provided that the action of further improving the solubility of the radiation-sensitive composition in an alkaline developer and suppressing the remaining undissolved material after development, etc.) Excluding the hydrogen donor).

  As the organic acid, an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in a molecule is preferable.

Examples of the aliphatic carboxylic acid include:
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, brasilic, methylmalonic, ethylmalonic, dimethylmalonic, methylsuccinic, tetramethylsuccinic Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;
Examples include aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

  Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to a phenyl group and a compound in which a carboxyl group is bonded to a phenyl group via a carbon chain.

Examples of phenyl group-containing carboxylic acids include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid and mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanic acid, and pyromellitic acid,
Examples include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidenic acid, coumaric acid, and umbellic acid.

  Among these organic acids, from the viewpoints of alkali solubility, solubility in a solvent described below, prevention of background fouling and film residue on a substrate or a light-shielding layer in an unexposed portion, an aliphatic carboxylic acid is an aliphatic carboxylic acid. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferred, and phthalic acid is particularly preferred.

  The organic acids can be used alone or in combination of two or more.

  The compounding amount of the organic acid is usually 15 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of each of the components (A) to (D) and the additive. In this case, if the amount of the organic acid exceeds 15 parts by weight, the adhesion of the formed colored layer to the substrate tends to decrease.

  The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.

Examples of the aliphatic amine include:
mono (cyclo) alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di- Di (cyclo) alkylamines such as -t-butylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyln-propylamine, diethyln-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri- tri (cyclo) alkylamines such as n-butylamine, tri-i-butylamine, tri-sec-butylamine and tri-t-butylamine;
Mono (cyclo) alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol and 4-amino-1-butanol;
Di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine and di-i-butanolamine;
Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine and tri-i-butanolamine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Amino (cyclo) alkanediols such as 2,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Examples thereof include aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, and 3-aminoisobutyric acid.

  Examples of the phenyl group-containing amine include a compound in which an amino group is directly bonded to a phenyl group, a compound in which an amino group is bonded to a phenyl group via a carbon chain, and the like.

Examples of phenyl group-containing amines include:
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, Aromatic amines such as N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples thereof include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  Of these organic amino compounds, mono (cyclo) alkanolamines are preferred as aliphatic amines from the viewpoints of solubility in a solvent described below, prevention of background contamination and film residue on the unexposed portion of the substrate or light-shielding layer, and the like. And amino (cyclo) alkanediols are preferred, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino -1,3-propanediol, 4-amino-1, 2-butanediol and the like are preferable, and as the phenyl group-containing amine, aminophenols are preferable. In particular, o-aminophenol, m-aminophenol, p- Aminophenol and the like are preferred.

  The organic amino compounds can be used alone or in combination of two or more.

  The compounding amount of the organic amino compound is usually 15 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the total of the components (A) to (D) and the additives. In this case, if the amount of the organic amino compound exceeds 15 parts by weight, the adhesion of the formed colored layer to the substrate tends to decrease.

Also, as other additives, for example,
A dispersing aid such as a blue pigment derivative or a yellow pigment derivative such as a copper phthalocyanine derivative;
Fillers such as glass and alumina;
High molecular compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylate);
Surfactants such as nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, An adhesion promoter such as 3-chloropropyl-methyl-dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones;
Anticoagulant such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

-(E) Solvent-
The solvent in the present invention disperses or dissolves the components (A) to (D) and additives constituting the radiation-sensitive composition, does not react with these components, and has appropriate volatility. As long as it can be selected and used as appropriate.

Examples of such a solvent include, for example,
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 Propylene glycol mono Chirueteru, dipropylene glycol mono -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 acetates 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, propylene glycol monoethyl ether acetate; diethylene glycol Other ethers such as dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone and cyclohexanone;

Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxyacetate Methyl-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-acetic acid -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , N-propyl pyruvate, methyl acetoacetate, acetoacetate Le, other esters such as ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be mentioned.

  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, diethylene glycol methyl Ethyl ether, 2-heptanone, 3-heptanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl -3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-propionate Butyl, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are more preferable, and propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, ethyl 3-ethoxypropionate, and 3-methoxybutyl acetate are more preferable. And cyclohexanone.

  The solvents may be used alone or in combination of two or more.

  Further, 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, diethyl oxalate And high boiling solvents such as diethyl maleate, [gamma] -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.

  These high-boiling 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 applicability of the obtained radiation-sensitive composition, stability and the like, the total concentration of each component excluding the solvent of the composition is preferably , 5 to 30% by weight, more preferably 10 to 20% by weight.

Characteristics of Radiation-Sensitive Composition for Color Filter The radiation-sensitive composition for color filters of the present invention has a surface tension of B (mN / m), a viscosity of A (mPa · s), and a colored layer. Assuming that the coating speed at the time of coating is V (m / s), the value (hereinafter referred to as “AV / B value”) obtained by the formula (A × V ÷ B) is less than 4.0 × 10 ⁻² . , Preferably 2.0 × 10 ^{−3 to} 3.5 × 10 ⁻² , particularly preferably 2.0 × 10 ^{−3 to} 3.0 × 10 ⁻² . In this case, when the AV / B value is 4.0 × 10 ⁻² or more, uneven coating tends to occur.

  When the radiation-sensitive composition for a color filter of the present invention has an AV / B value satisfying the above requirements, when forming a colored layer for a color filter on a substrate by a slit die coater, the discharge speed from a slit nozzle and A high balance with the wettability to the substrate can be ensured, and the color filter coloring layer having a uniform film thickness can be formed with high product yield and high efficiency without causing application unevenness.

  Further, the viscosity of the radiation-sensitive composition for a color filter of the present invention is preferably from 2.0 mPa · s to 8.0 mPa · s, particularly preferably from 2.0 mPa · s to 6.0 mPa · s.

Method for Forming Color Layer for Color Filter The method for forming the color layer for color filter of the present invention uses a radiation-sensitive composition for a color filter having the above-mentioned properties, and reduces the coating speed of the radiation-sensitive composition to 0.07 m. / S or more, a method of forming a color layer for a color filter on a substrate by a slit die coater.

  Hereinafter, the method for forming a colored layer for a color filter of the present invention will be described more specifically.

  First, on the surface of the substrate, if necessary, a light-shielding layer is formed so as to partition a portion where a pixel array is to be formed, and on this substrate, for example, a radiation-sensitive composition in which a red pigment is dispersed is slit. Coating with a die coater.

  Next, a coating film is formed by evaporating the solvent by performing a pre-bake, and after exposing the coating film through a photomask, it is particularly preferably developed using an alkali developer to remove an unexposed portion of the coating film. By dissolving and removing and then post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed.

  Next, using each radiation-sensitive composition in which a green or blue pigment is dispersed, coating, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and a blue pixel array. Are formed on the same substrate to obtain a colored layer in which pixel arrays of three primary colors of red, green and blue are arranged on the substrate.

  However, the order in which the pixel arrays of each color are formed in the present invention is not limited to the order described above.

  The coating thickness is preferably from 0.1 to 10 μm, more preferably from 0.2 to 8.0 μm, particularly preferably from 0.2 to 6.0 μm, as the thickness after removing the solvent.

  As the radiation used for forming the colored layer, for example, 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.

The exposure dose of radiation is preferably 10 to 10,000 J / m ² .

  Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [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. After the alkali development, the film 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 puddle) developing method, or the like can be applied. The development conditions are preferably at room temperature for 5 to 300 seconds.

  Examples of a substrate used when forming a colored layer in a color filter include, for example, glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, a ring-opening polymer of cyclic olefin, and hydrogenated hydrogen thereof. Additives and the like can be mentioned.

  Further, these 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, and a vacuum deposition, if desired.

Color Filter The color filter of the present invention has a colored layer formed from the radiation-sensitive composition for a color filter of the present invention.

  INDUSTRIAL APPLICABILITY The color filter of the present invention is extremely useful for a color image pickup tube element, a color sensor and the like in addition to a transmission type or reflection type color liquid crystal display device.

Color Liquid Crystal Display The color liquid crystal display of the present invention includes the color filter of the present invention.

  The color liquid crystal display device of the present invention can have an appropriate structure. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is arranged, and the driving substrate and the color filter substrate are opposed to each other with a liquid crystal layer interposed therebetween. it can. In addition, a substrate on which a color filter was formed on the surface of a driving substrate on which a thin film transistor (TFT) was arranged, and a substrate on which an ITO (tin-doped indium oxide) electrode was formed faced each other with a liquid crystal layer interposed therebetween. It can also be structured. The latter structure is characterized in that the aperture ratio can be significantly improved and a bright and high-definition display element can be obtained.

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

Example 1
(A) 40 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Red 254 and CI Pigment Yellow 139 as a pigment, and (B) methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenyl as an alkali-soluble resin. 70 parts by weight of a maleimide copolymer (copolymerization weight ratio = 15/15/35/10/25, Mw = 30,000, Mn = 10,000), (C) dipentaerythritol hexa as a polyfunctional monomer 80 parts by weight of acrylate, (D) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photoradical generator, and (E) propylene glycol monomethyl ether acetate as a solvent The composition (R1) was prepared by mixing 1,000 parts by weight. .

  For the composition (R1), the viscosity was measured by an EL viscometer (DVM-EII, manufactured by Toki Sangyo Co., Ltd .: The value measured at a measuring temperature of 25 ° C. and after 30 seconds at 20 rpm was defined as a viscosity value). It was 3.6 mPa · s, and the surface tension was 27 mN / m as measured by a dynamometer (manufactured by Shimadzu Corporation).

<Formation of coating film>
The composition (R1) was coated on a surface of a soda glass substrate (1,100 mm × 1,250 mm) on which a SiO ₂ film for preventing sodium ions from being eluted was formed, by a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd.). Using TR63210S-CL) at a coating speed of 0.07 m / s, 0.11 m / s or 0.15 m / s, a range of 1,080 mm × 1,230 mm (10 mm inward from each edge of the substrate, respectively) After that, the solvent was volatilized to produce three substrates each having a coating film having a thickness of 2.0 μm.

In this case, the AV / B value of the composition (R1) was 9.3 × 10 ⁻³ , 14.7 × 10 ^−3, and 20.0 × 10 ⁻³ according to the coating speed.

<Evaluation of coatability>
When the surface of the coated film after coating was irradiated with a sodium lamp and observed, no unevenness in appearance such as uneven streaks and uneven drying was observed in all regions, and good unevenness was observed. The results are shown in Table 1 with the case as bad.

  Further, as shown in FIG. 1, with respect to the coating film 2 formed in a region surrounded by a thin solid line having a thickness of 10 mm inward from each edge of the substrate 1, the edge portion of the coating film, the vicinity thereof, and the central portion are formed. When the film thickness was measured at a total of 35 measurement points (black circles) including the total, the variation of the film thickness was within ± 0.10 μm at all the measurement points, and excellent uniform coating properties were obtained. The results are shown in Table 1 as good when the variation of the film thickness was within ± 0.20 μm and uniform coating property was shown, and as poor when the variation of the film thickness was more than ± 0.20 μm. .

Example 2
(A) 60 parts by weight of a 60/40 (weight ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 138 as a pigment, and (B) methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenyl as an alkali-soluble resin. 70 parts by weight of a maleimide copolymer (copolymerization weight ratio = 15/15/35/10/25, Mw = 30,000, Mn = 10,000), (C) dipentaerythritol hexa as a polyfunctional monomer 80 parts by weight of acrylate, (D) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photo radical generator, and (E) 3-methoxybutyl acetate as a solvent 800 parts by weight were mixed to prepare a composition (R2).

Table 1 shows the results of measurement of the viscosity and surface tension of the composition (R2) in the same manner as in Example 1, and the AV / B value.
Table 1 shows the results of the evaluation of the coatability performed in the same manner as in Example 1.

Example 3
(A) 90 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Red 254 and CI Pigment Yellow 139 as a pigment; and (B) Methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenyl as an alkali-soluble resin. 70 parts by weight of a maleimide copolymer (copolymerization weight ratio = 15/15/35/10/25, Mw = 15,000, Mn = 6,000), (C) dipentaerythritol hexa as a polyfunctional monomer 80 parts by weight of acrylate, (D) 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photoradical generator, and (E) propylene glycol monomethyl ether acetate as a solvent The composition (R3) was prepared by mixing 1,500 parts by weight.

Table 1 shows the results of measuring the viscosity and surface tension of the composition (R3) in the same manner as in Example 1, and the AV / B value.
Table 1 shows the results of the evaluation of the coatability performed in the same manner as in Example 1.

Example 4
(A) 100 parts by weight of a 60/40 (weight ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 138 as a pigment; (B) Methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenyl as an alkali-soluble resin 70 parts by weight of a maleimide copolymer (copolymerization weight ratio = 15/15/35/10/25, Mw = 12,000, Mn = 5,000), (C) dipentaerythritol hexa as a polyfunctional monomer 80 parts by weight of acrylate, (D) 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photoradical generator, and (E) 3-methoxybutyl acetate as a solvent The composition (R4) was prepared by mixing 1,200 parts by weight.

Table 1 shows the results of measurement of the viscosity and surface tension of the composition (R4) in the same manner as in Example 1, and the AV / B value.
Table 1 shows the results of the evaluation of the coatability performed in the same manner as in Example 1.

Example 5
A composition (R5) was prepared in the same manner as in Example 1 except that the amount of propylene glycol monomethyl ether acetate was changed to 700 parts by weight.

Table 1 shows the results of measurement of the viscosity and surface tension of the composition (R5) in the same manner as in Example 1, and the AV / B value.
Table 1 shows the results of the evaluation of the coatability performed in the same manner as in Example 1.

Example 6
(A) 80 parts by weight of a 90/10 (weight ratio) mixture of CI Pigment Red 254 and CI Pigment Red 177 as a pigment, and (B) methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenyl as an alkali-soluble resin 60 parts by weight of a maleimide copolymer (copolymerization weight ratio = 15/20/30/10/25, Mw = 15,000, Mn = 6,000), (C) dipentaerythritol hexa as a polyfunctional monomer 90 parts by weight of acrylate, (D) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 / 2,2'-bis (2,4-dichlorophenyl) -4 as a photoradical generator , 4 ', 5,5'-Tetraphenyl-1,2'-biimidazole / 2-mercaptobenzothiazole / 4,4 40 parts by weight of a 30/4/2/4 (weight ratio) mixture of '-bis (diethylamino) benzophenone, and (E) 50/50 (weight ratio) of ethyl 3-ethoxypropionate / propylene glycol monomethyl ether acetate as a solvent. The composition (R6) was prepared by mixing 1,400 parts by weight.

Table 1 shows the results of measurement of the viscosity and surface tension of the composition (R6) in the same manner as in Example 1, and the AV / B value.
Table 1 shows the results of the evaluation of the coatability performed in the same manner as in Example 1.

Example 7
(A) 80 parts by weight of a 97/3 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a pigment, and (B) methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N as an alkali-soluble resin 65 parts by weight of a phenylmaleimide copolymer (copolymerization weight ratio: 15/15/30/10/30, Mw = 12,000, Mn = 5,000), (C) dipentane as a polyfunctional monomer 85 parts by weight of erythritol hexaacrylate, (D) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1 / 2,2'-bis (2,4-dichlorophenyl)-as a photoradical generator 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole / 2-mercaptobenzothiazole / 4,4 40 parts by weight of a 30/3/2/5 (weight ratio) mixture of '-bis (diethylamino) benzophenone, and (E) ethyl 3-ethoxypropionate / propylene glycol monomethyl ether acetate / diethylene glycol methyl ethyl ether as a solvent 1600 parts by weight of 45/40/15 (weight ratio) were mixed to prepare a composition (R7).

Table 1 shows the results of measurement of the viscosity and surface tension of the composition (R7) in the same manner as in Example 1, and the AV / B value.
Table 1 shows the results of the evaluation of the coatability performed in the same manner as in Example 1.

It is a figure explaining the measuring point of a film thickness.

Explanation of reference numerals

1 substrate 2 coating

Claims (5)

In a radiation-sensitive composition containing (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photoradical generator, and (E) a solvent, the viscosity is defined as A (mPa S), when the surface tension is B (mN / m) and the coating speed for forming the colored layer is V (m / s), the value obtained by the formula (A × V ÷ B) Is less than 4.0 × 10 ^-2 , the radiation-sensitive composition for a color filter used for coating with a slit die coater. The radiation-sensitive composition for a color filter according to claim 1, wherein the viscosity of the radiation-sensitive composition is in a range of 2.0 mPa · s to 8.0 mPa · s. A color filter having a colored layer formed from the radiation-sensitive composition for a color filter according to claim 1. A color liquid crystal display device comprising the color filter according to claim 3. A method for forming a colored layer on a substrate using the radiation-sensitive composition for a color filter according to claim 1 or 2, wherein a coating speed of the radiation-sensitive composition is 0.07 m / s. A method for forming a colored layer for a color filter using a slit die coater, which is characterized by the above.

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