JP4496818B2 - Radiation sensitive composition for color filter, color filter, and color liquid crystal display device - Google Patents

Description

  The present invention relates to a radiation-sensitive composition for color filters, a color filter, and a color liquid crystal display device, and more specifically, manufacture of a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. The present invention relates to a radiation sensitive composition for color filters useful for, a color filter formed from the radiation sensitive composition for color filter, and a color liquid crystal display device comprising the color filter.

In producing a color filter using a colored radiation-sensitive composition, a film of the colored radiation-sensitive composition is usually formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance. A formation method (for example, for obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having a pattern shape, developing and dissolving and removing unexposed portions, and then post-baking (for example, Patent Document 1 and Patent Document 2) are known.
A color liquid crystal display device having a color filter is required to have high brightness, and therefore, in recent years, a color filter is increasingly required to have a high light transmittance. In recent years, with the spread of digital video cameras and high-definition televisions, there has been an increasing demand for high color density color display of color liquid crystal display devices, such as displaying deep blue and bright sunsets like the winter sea. ing. In order to display a high color density color, if the “blackness” of the black display portion is not clearly displayed, the screen is blurred and has no sharpness. For this reason, pixels or colored layers with higher contrast are required for high color density color display.

In response to such requirements, generally, a method of using a pigment atomized by a grinding method or a precipitation method, a method of atomizing a pigment by optimizing a dispersion process such as optimizing a dispersion bead diameter or dispersion time, etc. Etc. are known to be effective. However, as the atomization of the pigment progresses, the pigment tends to aggregate due to an increase in the particle surface area, and it becomes difficult to obtain a pigment dispersion that generally has a low viscosity and is difficult to increase in viscosity over time. On the other hand, in order to prevent the aggregation of the pigment, a method of adding a surfactant or a resin having an adsorption ability to the pigment as a dispersant has been proposed. However, there are many cases where sufficient contrast and storage stability cannot be achieved even when a dispersant is used, and there is a problem that developability is remarkably lowered with an increase in the addition amount thereof.
Therefore, in recent years, there has been a strong demand for development of a radiation sensitive composition for color filters having high light transmittance, high contrast, and excellent developability and storage stability.

JP-A-2-144502 JP-A-3-53201

  The subject of this invention is providing the radiation sensitive composition for color filters which has high contrast and was excellent in developability, storage stability, etc.

The present invention, first,
A radiation-sensitive composition for a color filter containing (A) a pigment, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photopolymerization initiator, and (F) a solvent. (B) dispersant is (A) pigment, (B) dispersant, (C) alkali-soluble resin, (D) polyfunctional monomer, (E) photopolymerization initiator, and (F) A radiation-sensitive composition for a color filter containing a solvent, wherein (B) the dispersant has an amine value (unit mgKOH / g)> 0 and an acid value (unit mgKOH / g) = 0 obtained by living anion polymerization and the acrylic copolymer as essential components, the 3 to 35 parts by der usage relative to (a) the pigment 100 parts by weight of the acrylic copolymer Ri, (C) an alkali-soluble resin (meth) acrylic Acid / 2-hydroxyethyl (meth) acrylate / benzyl (Meth) acrylate / polymethyl (meth) acrylate polymer Macromonomer copolymer having a mono (meth) acryloyl group at the end of the molecular chain and / or (meth) acrylic acid / ω-carboxydicaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N- phenylmaleimide copolymer color filter radiation-sensitive composition characterized that you contain,
Consists of.

  Secondly, the present invention comprises a color filter formed from the radiation sensitive composition for color filter.

  Thirdly, the present invention comprises a liquid crystal display device comprising the color filter.

Hereinafter, the present invention will be described in detail.
Radiation sensitive composition for color filter- (A) Pigment-
The pigment in the present invention is not particularly limited, and may be either an organic pigment or an inorganic pigment. However, since the color filter is required to have high purity and high permeability color development and heat resistance, it is particularly an organic pigment. Is preferred.
Examples of the organic pigment include a color index (CI; The Society of Dyers).
and Colorists (published by and Colorists)), specifically, those with the following color index (CI) numbers.

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 185, 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 243, 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 admixture 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 the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
These inorganic pigments can be used alone or in admixture of two or more.
Furthermore, in the present invention, if necessary, one or more dyes or natural pigments can be used in combination with the pigment.

-(B) Dispersant-
The dispersant in the present invention is an acrylic copolymer (unit mgKOH / g, hereinafter the same)> 0 and acid value (unit mgKOH / g, the same hereinafter) = 0 obtained by living anion polymerization (hereinafter, the same). , “Acrylic dispersant (B1)”) as an essential component.

The amine value of the acrylic dispersant (B1) exceeds 0, preferably 0.5 to 10, and more preferably 2 to 6. In this case, when the amine value of the acrylic dispersant (B1) is 0 (zero), the dispersibility of the pigment and the storage stability of the resulting composition tend to decrease.
Further, the acid value of the acrylic dispersant (B1) must be 0 (zero). In this case, if the acrylic dispersant (B1) has an acid value, even if the amine value exceeds 0, it becomes difficult to finely disperse the pigment and the contrast tends to decrease.

Examples of commercially available acrylic dispersants (B1) include Disperbyk-2000 (amine value = 4, manufactured by BYK Corporation (BYK)).
In this invention, an acrylic type dispersing agent (B1) can be used individually or in mixture of 2 or more types.

In the present invention, other dispersants can be used in combination with the acrylic dispersant (B1).
Examples of the other dispersant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), Fuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (above, Asahi Glass Co., Ltd.), Disperbyk-101, -103, -107, Same-110, Same-111, Same-115, Same-130, Same-160, Same-161, Same-162, Same-163, Same-164, Same-165, Same-166, Same-170, Same- 180, -182, -2001 (above, manufactured by Big Chemie Japan Co., Ltd.), Solsperse S5000, 12000, 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000 27000, 28000 (above, manufactured by Avicia Co., Ltd.), EFKA46, 47, 48, 745, 4540 4550, 6750, EFKA LP4008, 4009, 4010, 4015, 4015, 4050, 4055, 4560, 4800, EFKA Polymer400, 401, 402, 403, 450, 451, 453 (The above, manufactured by Fuka Chemicals Co., Ltd.), Ajispa-PB-822 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.
These other dispersants can be used alone or in admixture of two or more.

  The use ratio of the other dispersant is usually 0 to 75% by weight, preferably 0 to 50% by weight, based on the total amount of the acrylic dispersant (B1) and the other dispersant. In this case, if the use ratio of the other dispersant exceeds 75% by weight, there is a possibility that a good balance of contrast, developability and storage stability cannot be secured.

  The usage-amount (solid content conversion) of the acrylic type dispersing agent (B1) in this invention is 3-35 weight part with respect to 100 weight part of (A) pigment, Preferably it is 10-30 weight part. In this case, if the amount of the acrylic dispersant (B1) used is less than 3 parts by weight, the contrast and storage stability may be impaired, whereas if it exceeds 35 parts by weight, the alkali developability may be impaired.

-(C) Alkali-soluble resin-
The alkali-soluble resin in the present invention has a mono (meth) acryloyl group at the end of a polymer molecular chain of (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate. Macromonomer copolymer and / or (meth) acrylic acid / ω-carboxydicaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer , a resin having a solubility in an alkali developing solution used in (a) when acting as a binder of the pigment, and the production of color filters, the development processing step.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the alkali-soluble resin is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In this case, when the copolymerization ratio is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to be reduced, whereas when it exceeds 50% by weight, the solubility in an alkali developer is low. When the development is performed with an alkaline developer, the pixel tends to drop off from the substrate or the surface of the pixel becomes rough.

Mw measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of an alkali-soluble resin is usually 3,000 to 300,000, preferably 5,000 to 100,000.
Moreover, Mn measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin is 3,000-60,000 normally, Preferably it is 5,000-25,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin is usually 1 to 5, preferably 1 to 4.
In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition having excellent developability can be obtained, and thereby a pixel pattern having sharp pattern edges can be obtained. In addition to being able to be formed, residues, background stains, film residues and the like are less likely to occur on the unexposed substrate and the light shielding layer during development.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
The usage-amount of the alkali-soluble resin in this invention is 10-1,000 weight part normally with respect to 100 weight part of (A) pigments, Preferably it is 20-500 weight part. 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 be lowered, or background stains or film residues may be generated on the substrate or the light shielding layer in the unexposed area. When the amount exceeds 1,000 parts by weight, the pigment concentration is relatively lowered, and it may be difficult to achieve the target color concentration as a thin film.

-(D) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As the multifunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like and their dicarboxylic acid modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexa are particularly preferable. Acrylates are preferred in that they are excellent in strength and surface smoothness of the colored layer, and are less likely to cause background stains and film residue on the unexposed substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (C) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is reduced. There is a tendency that background stains, film residues, etc. are likely to occur on the unexposed substrate or on the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include monomers similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for (C) the alkali-soluble resin, and N- (meta ) In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, trade names include M-5600 (manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more.

  The proportion of the monofunctional monomer used in the present invention is usually 90% by weight or less, preferably 50% by weight or less, based on the total amount of the polyfunctional monomer and the monofunctional monomer. . In this case, if the proportion of the monofunctional monomer used exceeds 90% by weight, the strength and surface smoothness of the pixel may be insufficient.

  The total amount of the polyfunctional monomer and the monofunctional monomer used in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight, with respect to 100 parts by weight of the (C) alkali-soluble resin. Part. In this case, if the total amount used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be lowered. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is lowered or There is a tendency that soiling, film residue, and the like are likely to occur on the substrate or the light shielding layer.

-(E) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (D) polyfunctional monomer and the monofunctional monomer used in some cases by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. It is a compound capable of generating active species capable of initiating polymerization.
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. A compound etc. can be mentioned.
In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, acetophenone compounds, biimidazole compounds and triazine compounds can be used. At least one selected from the group is preferred.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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 etc. can be mentioned.
Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone -1 etc. are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (D) polyfunctional monomer and the monofunctional monomer. 0.01 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight. In this case, if the amount of the acetophenone compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a colored layer in which the pixel pattern is arranged according to a predetermined arrangement, If it exceeds 100 parts by weight, the formed pixels tend to fall off the substrate during development.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 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'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 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 and the like can be mentioned. .

Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are more preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole is preferred.
The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved matter and precipitates, has high sensitivity, and sufficiently proceeds with a curing reaction by exposure with a small amount of energy, and is not exposed. Therefore, the exposed coating is clearly divided into a hardened portion that is insoluble in the developer and an uncured portion that has a high solubility in the developer. A high-definition colored layer 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 admixture of two or more.

  In the present invention, the amount used in the case of using a biimidazole compound as a photopolymerization initiator is usually (D) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer, 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of biimidazole compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a colored layer 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 pixels tend to fall off the substrate during development.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate 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 is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, these hydrogen donors will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, 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 are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based 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 heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In addition, in the amine-based 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 group may be substituted at a position other than the amino 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, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Of these amine-based 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 a biimidazole compound.

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed pixels are difficult to drop off from the substrate during development, and that the pixels have high strength and sensitivity.
Specific examples of a preferred combination of a mercaptan hydrogen donor and an amine 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 are further preferable combinations. Are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the particularly preferred combination is 2-mercaptobenzothi Is a tetrazole / 4,4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 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 preferably 0 with respect to 100 parts by weight of the total of (D) the polyfunctional monomer and the monofunctional monomer. 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. On the other hand, if it exceeds 40 parts by weight, the formed pixels are likely to fall off the substrate during development. Tend.

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 (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- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.
Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, when the triazine-based compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (D) polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of the triazine compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a colored layer in which a pixel pattern is arranged according to a predetermined arrangement, If it exceeds 40 parts by weight, the formed pixels tend to drop off from the substrate during development.

-Additive component-
The radiation sensitive composition for a color filter in the present invention may contain various additive components as necessary.
The additive component may be an organic acid or an organic amino compound (provided to improve the solubility of the radiation-sensitive composition in an alkaline developer and to further suppress the remaining undissolved product after development) , Excluding the hydrogen donor).

The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
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 acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid , Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Examples thereof include aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and compounds in which a carboxyl group is bonded to a phenyl group via a divalent carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, and prevention of soiling and film residue on the substrate and the light shielding layer in the unexposed area. Dicarboxylic acids are preferred. In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are 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 admixture of two or more.
The amount of the organic acid used 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 (E) and the additive component. In this case, when the amount of the organic acid used exceeds 15 parts by weight, the adhesion of the formed pixel to the substrate tends to be lowered.

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;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec- Di (cyclo) alkylamines such as butylamine and di-t-butylamine;
Dimethyl ethylamine, methyl diethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, tri-n-propylamine, tri -Tri (cyclo) alkylamines such as i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine;

Mono (cyclo) alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol;
Di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine;
Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, 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-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 compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a divalent carbon chain.
As the phenyl group-containing amine, for example,
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.

Among these organic amino compounds, mono (cyclo) alkanolamine is used as the aliphatic amine from the viewpoints of solubility in a solvent described later, prevention of soiling and film residue on the unexposed substrate and the 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, and as the phenyl group-containing amine, aminophenols are preferable, and in particular, o-aminophenol, m-aminophenol, p- Aminophenol and the like are preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used 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 (E) and the additive component. In this case, when the usage-amount of an organic amino compound exceeds 15 weight part, there exists a tendency for the adhesiveness with the board | substrate of the formed pixel to fall.

Moreover, as an additive component other than the above, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl-methyl-dimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Adhesion promoters such as 3-chloropropyl, methyl, dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents 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.

(F) Solvent As the solvent in the present invention, the components (A) to (E) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components, and have an appropriate volatility. As long as it has, it can be appropriately selected and used.
As such a solvent, for example,
Alcohols such as methanol, ethanol, benzyl alcohol;
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, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono- - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly) alkylene glycol monoalkyl ethers such as monoethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methyl-3-methoxybutyl acetate, n-butyl propionate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, 2 -Methyl hydroxy-3-methylbutyrate, ethyl 2-oxobutyrate, etc. Other esters;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, benzyl alcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol from the viewpoints of solubility, pigment dispersibility, coatability, etc. Mono-n-butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, n-butyl acetate I-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methyl Xylbutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3- Methoxybutyl propionate, 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 solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ- A high boiling point solvent such as butyrolactone, ethylene carbonate, propylene carbonate, or ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.
The amount of solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is preferable from the viewpoints of applicability and storage stability of the resulting radiation-sensitive composition. Is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

Method for Forming Color Filter Next, a method for forming the color filter of the present invention using the radiation sensitive composition for color filters of the present invention (hereinafter also simply referred to as “radiation sensitive composition”) will be described. .
The method for forming a color filter of the present invention includes at least the following steps (1) to (4).
(1) The process of forming the film of the radiation sensitive composition of this invention on a board | substrate.
(2) A step of exposing radiation to at least a part of the coating.
(3) A step of developing the film after exposure.
(4) A step of post-baking the film after development.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to divide the pixel forming portion, and after applying the radiation-sensitive composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When the radiation-sensitive composition is applied to the substrate, an appropriate application method such as spin coating, cast coating or roll coating can be employed, but a coating method using a spin coater or a slit die coater is preferred.
The prebaking condition is usually about 2 to 4 minutes at 70 to 110 ° C.
The coating thickness is usually 0.1 to 8.0 μm, preferably 0.2 to 6.0 μm, and more preferably 0.2 to 4.0 μm, as the film thickness after drying.

-(2) Process-
Next, radiation is exposed to at least a part of the formed film. When exposing a part of the film in this step, the exposure is usually performed through a photomask having a predetermined pattern.
As radiation used for exposure, for example, radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray can be appropriately selected and used, but radiation having a wavelength in the range of 190 to 450 nm can be used. preferable.
Exposure of radiation is usually, 10~10,000J / m ² approximately.

-(3) Process-
Next, the exposed film is developed using a developer, preferably an alkali developer, and the unexposed portion of the film is dissolved and removed to form a predetermined pattern.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of 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 alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The development conditions are preferably about 5 to 300 seconds at room temperature.

-(4) Process-
Subsequently, the substrate on which the pixel pattern is arranged in a predetermined arrangement can be obtained by post-baking the developed film.
As post-baking processing conditions, 180-240 degreeC and about 15-90 minutes are preferable. The film thickness of the pixel thus formed is usually 0.1 to 6.0 μm, preferably 0.5 to 3.0 μm.

By repeating the steps (1) to (4) using each radiation sensitive composition in which red, green or blue pigments are dispersed, red, green and blue pixel patterns are formed on the same substrate. Accordingly, a colored layer in which pixel patterns of the three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate.
In the present invention, the order of forming the pixel patterns of the respective colors can be arbitrarily selected.

Color filter The color filter of the present invention is formed from the radiation-sensitive composition for a color filter of the present invention.
The color filter of the present invention is extremely useful for color imaging tube elements, color sensors, etc., in addition to transmissive or reflective color liquid crystal display devices.

Color liquid crystal display device The color liquid crystal display device of the present invention comprises a color filter formed from the radiation-sensitive composition for a color filter of the present invention.
The color liquid crystal display device of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other through the liquid crystal layer. Furthermore, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed include a liquid crystal layer. It is also possible to adopt a structure facing each other. The latter structure has the advantage that the aperture ratio can be remarkably improved and a bright and high-definition liquid crystal display device can be obtained.

The radiation sensitive composition for a color filter of the present invention has a high contrast and is excellent in developability, storage stability and the like.
Therefore, the radiation sensitive composition for color filters of the present invention can be used very suitably for the formation of various color filters including color filters for color liquid crystal display devices in the electronic industry.

Hereinafter, the 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) CI Pigment Red 254 / CI Pigment Red 177 = 50/50 (weight ratio) mixture 100 parts by weight as a pigment, (B) Disperbyk-2000 (solid content concentration 46.2% by weight) 40 parts by weight (as a dispersant) About 18.48 parts by weight in terms of solid content), (C) methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer (copolymer weight ratio = 15/15/60 / 10, Mw = 20,000, Mn = 10,000) 100 parts by weight, (D) 100 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (E) 2-benzyl-2 as a photopolymerization initiator 40 parts by weight of dimethylamino-1- (4-morpholinophenyl) -butanone-1, (F) As a solvent, 500 parts by weight of propylene glycol monomethyl ether acetate, 670 parts by weight of ethyl 3-ethoxypropionate, and 30 parts by weight of propylene glycol monomethyl ether were mixed to prepare a radiation sensitive composition.

Example 2
As the dispersant (B) in Example 1, Disperbyk-2000 was replaced with 40 parts by weight, Disperbyk-2000 was 30 parts by weight (approximately 13.86 parts by weight in terms of solid content) and Disperbyk-165 (amine number = 15, A radiation-sensitive composition was prepared in the same manner as in Example 1, except that 30 parts by weight (acid content = 0, solid content concentration 39.6% by weight) (about 11.88 parts by weight in terms of solid content) was used. .

Example 3
(A) 100 parts by weight of CI Pigment Blue 15 as a pigment, (B) 60 parts by weight of Disperbyk-2000 as a dispersant (approximately 27.72 parts by weight in terms of solid content), (C) Methacrylic acid / ω as an alkali-soluble resin -Carboxydicaprolactone monoacrylate / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide copolymer (copolymerization weight ratio = 15/10/10/35/10/20, Mw = 6,000, Mn = 3 , 000) 120 parts by weight, (D) 150 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 2-methyl- (4-methylthiophenyl) -2-morpholino-1 as a photopolymerization initiator. -60 parts by weight of propanone-1 and (F) propylene glycol as solvent A radiation-sensitive composition was prepared by mixing 650 parts by weight of monomethyl ether acetate, 800 parts by weight of 3-methoxybutyl acetate and 50 parts by weight of propylene glycol monoethyl ether.

Example 4
As the dispersant (B) in Example 3, Disperbyk-2000 was replaced by 60 parts by weight, Disperbyk-2000 was 30 parts by weight (solid content conversion: about 13.86 parts by weight) and Disperbyk-2001 (amine number = 29, A radiation-sensitive composition was prepared in the same manner as in Example 3 except that 30 parts by weight (acid content = 19, solid content concentration 45.1% by weight) (about 13.53 parts by weight as solid content) was used. .

Comparative Example 1
In the same manner as in Example 1 except that 20 parts by weight of Solsperse S24000 (amine value = 50, acid value = 25) was used instead of Dispersbyk-2000 (B) dispersant in Example 1 instead of 40 parts by weight. Thus, a radiation sensitive composition was prepared.

Comparative Example 2
The radiation-sensitive composition was the same as in Example 1 except that the amount of Dispersbyk-2000 (B) dispersant used in Example 1 was changed to 80 parts by weight (about 36.96 parts by weight in terms of solid content). A product was prepared.

Comparative Example 3
Dispersbyk-2000 (B) dispersant in Example 3 was replaced with 60 parts by weight, and Disperbyk-165 (amine value = 15, acid value = 0, solid content concentration 39.6% by weight) 70 parts by weight (solid A radiation-sensitive composition was prepared in the same manner as in Example 3 except that about 28 parts by weight in terms of minutes) was used.

Comparative Example 4
In the same manner as in Example 3, except that Dispersbyk-2000 (B) dispersant in Example 3 was replaced by 60 parts by weight, and 90 parts by weight of Disperbyk-165 (about 36 parts by weight in terms of solid content) was used. A radiation sensitive composition was prepared.

Evaluation The radiation-sensitive compositions of each Example and each Comparative Example were evaluated in the following manner. The evaluation results are shown in Table 1.
Evaluation of developability:
Each radiation-sensitive composition was applied on the surface of a # 1737 glass substrate manufactured by Corning using a spin coater, and then pre-baked at 90 ° C. for 3 minutes to form a film having a thickness of 2.0 μm. Then, after cooling the substrate to room temperature, using a high-pressure mercury lamp (illuminance: 250 W / m ² ), ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm are applied to the coating through a photomask at 1,000 J / m ^2. The exposure amount was as follows. Thereafter, a developer CD150CR manufactured by JSR Co., Ltd. at 23 ° C. (including 0.04% by weight of potassium hydroxide) was used as the developer, and the developer discharge pressure was 0.1 MPa (nozzle diameter 1.0 mm) for 1 minute. After performing shower development, the substrate was washed with ultrapure water and further post-baked at 200 ° C. for 30 minutes to form a red stripe pixel pattern on the substrate.
Next, the obtained pixel pattern is observed, and “▲” indicates that a residue or background stain is observed on the substrate of the unexposed portion, “△” indicates that the pixel pattern is missing or peeled, and “ “X” indicates a residue or background stain on the substrate and chipping or peeling on the pixel pattern. No residue or background stain is found on the unexposed substrate, and the pixel pattern is chipped or peeled off. The case where no was recognized was evaluated as “◯”.

Contrast evaluation:
The substrate on which the pixel pattern is formed is sandwiched between two deflecting plates, and the front-side deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the maximum and minimum values of transmitted light intensity The value was measured, and the ratio (maximum value / minimum value) between the maximum value and the minimum value was calculated and evaluated. At this time, when the value of the ratio is 2000 or more, it can be said that the contrast is good.

Evaluation of storage stability:
About each radiation sensitive composition, the initial viscosity was measured using the Tokyo Keiki E-type viscosity meter. Further, 50 g of each radiation sensitive composition was put in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity after standing was measured using an E-type viscometer manufactured by Tokyo Keiki. At this time, the rate of change of the viscosity after standing with respect to the initial viscosity is calculated, “◯” when the rate of change is less than 5%, “Δ” when 5% or more and less than 10%, “×” was evaluated.

Claims (3)

A radiation-sensitive composition for a color filter containing (A) a pigment, (B) a dispersant, (C) an alkali-soluble resin, (D) a polyfunctional monomer, (E) a photopolymerization initiator, and (F) a solvent. And (B) an acrylic copolymer having an amine value (unit mgKOH / g)> 0 and an acid value (unit mgKOH / g) = 0 obtained by living anionic polymerization as a dispersant is an essential component, the amount of the acrylic copolymer 3 to 35 parts by der respect (solid basis) of (a) the pigment 100 parts by weight of Ri, (C) an alkali-soluble resin (meth) acrylic acid / 2-hydroxyethyl Polymer of (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate Macromonomer copolymer having mono (meth) acryloyl group at the end of molecular chain and / or (meth) acryl / .Omega. carboxymethyl dicaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N- phenylmaleimide copolymer Rukoto color filter radiation-sensitive composition according to claim to contain object.   A color filter formed from the radiation-sensitive composition for a color filter according to claim 1.   A liquid crystal display device comprising the color filter according to claim 2.