JP5663823B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a liquid crystal display element. More specifically, the present invention is useful for 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 used for forming a colored layer, a color filter including a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display element including the color filter.

  As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (Patent Documents 1 to 3) 2) is known.

  In recent years, in the technical field of color filters, it has become mainstream to reduce the exposure amount to shorten the tact time, and has sufficient development resistance, solvent resistance, etc. even at a low exposure amount, that is, a colored layer. There is a demand for higher sensitivity of the radiation-sensitive composition for forming. In particular, regarding solvent resistance, the problem of elution of colored components from the color filter is becoming apparent, and it is required to solve this problem.

In order to meet the recent demands for high contrast, high brightness, and high color purity for color liquid crystal display elements, various pigments used in colored layer-forming radiation-sensitive compositions have various backgrounds. It is considered that there is a tendency that the proportion of the pigment occupying in the radiation-sensitive composition for forming the colored layer tends to be higher and higher.
As a means for increasing the sensitivity of the radiation-sensitive composition for forming a colored layer, for example, polymerization having 7 or more (meth) acryloyloxy groups and 1 or more carboxyl groups in a photosensitive resin composition for a color filter. It is known to contain a functional compound (Patent Document 3).
However, it has not been possible to sufficiently solve the above-described problem of elution of the colored components.
JP-A-2-144502 JP-A-3-53201 JP 2007-279720 A

  An object of the present invention is to provide a radiation-sensitive composition for forming a colored layer that can form a pixel and a black matrix having sufficient development resistance even at a low exposure amount and having excellent solvent resistance. There is.

  As a result of intensive studies, the present inventors have included a specific polymerizable compound in the radiation-sensitive composition for forming a colored layer, thereby having sufficient development resistance even at a low exposure amount. The present inventors have found that a radiation-sensitive composition for forming a colored layer capable of forming a pixel and a black matrix having excellent solvent properties can be obtained.

  That is, the present invention firstly provides a radiation-sensitive composition for forming a colored layer, which contains (A) a colorant, (B) an alkali-soluble resin, (C) a polymerizable compound, and (D) a photopolymerization initiator. And (C) at least one selected from the group consisting of a dendrimer having two or more polymerizable reactive groups at its terminal and a hyperbranched polymer as a polymerizable compound, for forming a colored layer A radiation-sensitive composition is provided.

Secondly, the present invention provides a color filter comprising a colored layer formed using the radiation-sensitive composition.
Thirdly, the present invention provides a color liquid crystal display device comprising the color filter.

According to the radiation-sensitive composition for forming a colored layer of the present invention, a pixel and a black matrix having sufficient development resistance and excellent solvent resistance can be formed even at a low exposure amount.
Therefore, the radiation-sensitive composition of the present invention can be suitably used for the production of various color filters including color filters for color liquid crystal display devices and color filters for color separation of solid-state imaging devices in the electronic industry. it can.

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for forming colored layer “Colored layer” in the radiation-sensitive composition for forming a colored layer of the present invention (hereinafter also referred to as “radiation-sensitive composition”) refers to a pixel used for a color filter, and Means a layer made of black matrix.
“Radiation” means electromagnetic waves including visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
Hereafter, the structural component of the radiation sensitive composition for colored layer formation of this invention is demonstrated.

-(A) Colorant-
The colorant (A) in the present invention is not particularly limited and may be either an organic pigment or an inorganic pigment.
Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (CI). Listed are numbers.

  C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 211;

  C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

  C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  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, for example, 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 colorants may be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876, and various commercially available polymers or oligomers for dispersing pigments. The polymer coating method on the carbon black surface is disclosed in, for example, JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like.
The colorants can be used alone or in admixture of two or more.

When the radiation-sensitive composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development and heat resistance, (A) the coloring agent has high color development and high heat resistance. An agent, particularly a colorant having high heat decomposition resistance is preferable, specifically an organic colorant is preferable, and an organic pigment is particularly preferably used.
On the other hand, when the radiation-sensitive composition of the present invention is used for forming a black matrix, since the black matrix is required to have light shielding properties, an organic pigment or carbon black is preferably used as the colorant (A).
Moreover, the radiation sensitive composition of this invention is C.I. I. Pigment red 254, C.I. I. This is particularly useful in improving the solvent resistance of a colored layer formed using a radiation-sensitive composition containing at least one selected from the group consisting of CI Pigment Green 58 and carbon black.

  The radiation-sensitive composition of the present invention has excellent solvent resistance even when the content of the colorant is 30% by weight or more in the total solid content of the radiation-sensitive composition. In the present invention, the upper limit of the content of the colorant is preferably 60% by weight or less, particularly preferably 50% by weight or less in the total solid content of the radiation-sensitive composition from the viewpoint of ensuring developability. . Here, solid content is components other than the solvent mentioned later.

The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired.
As the dispersant, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.

Such a dispersant can be obtained commercially, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation) as a modified acrylic copolymer, Disperbyk-161 as polyurethane, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), EFKA4046 (manufactured by Ciba Specialty Chemicals), Solsperse 76500 (manufactured by Lubrizol Corporation) As a cationic comb-shaped graft polymer, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), Ajisper PB821, Ajisper PB822 (Ajinomoto Fine Techno Co., Ltd.) Mention may be made of the Company, Ltd.), and the like.

These dispersants can be used alone or in admixture of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, and particularly preferably 10 to 100 parts by weight with respect to 100 parts by weight of the (A) colorant. 50 parts by weight. In this case, when the content of the dispersant exceeds 100 parts by weight, developability and the like may be impaired.

  Examples of the dispersion aid include a blue pigment derivative and a yellow pigment derivative. Specific examples include a copper phthalocyanine derivative.

-(B) Alkali-soluble resin-
As the (B) alkali-soluble resin in the present invention, the developer (A) acts as a binder for the colorant and is used in a developing step for producing a color filter, particularly preferably an alkali developer. There is no particular limitation as long as it has solubility. Among them, 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 other co-polymers. A copolymer (hereinafter referred to as “carboxyl group-containing copolymer”) with a polymerizable ethylenically unsaturated monomer (hereinafter referred to as “copolymerizable unsaturated monomer”) is preferred.

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;
Mono [(meth) acryloyloxyalkyl] of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.
In the present invention, the carboxyl group-containing unsaturated monomer is preferably (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, Particularly preferred is (meth) acrylic acid.

  In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer 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.

Examples of the copolymerizable unsaturated monomer include:
Maleimide;
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- N-substituted maleimides such as succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinyl Phenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether , Aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Unsaturated carboxylic acid esters such as glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

In the present invention, examples of the copolymerizable unsaturated monomer include N-position substituted maleimide, aromatic vinyl compound, unsaturated carboxylic acid ester, macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain, and the like. In particular, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol , Polystyrene macromonomer, polymethylmethacrylate macromonomer and the like are preferable.

As a preferable specific example of (B) alkali-soluble resin in the present invention,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / Nm-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / p-hydroxy-α-methylstyrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / paracumylphenol ethylene oxide modified (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / phenyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / Nm-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / Np-hydroxyphenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer and the like.

  In the present invention, for example, an alkali-soluble resin obtained by copolymerization of a copolymerizable unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is added to an alkali-soluble resin such as 2- (meth) acryloyloxyethyl isocyanate. By reacting the saturated isocyanate compound, a polymerizable unsaturated bond can be introduced into the side chain of the alkali-soluble resin.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 1,000 to 45,000, preferably Is 3,000 to 30,000.
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 in the present invention is usually 1,000 to 45,000. , Preferably 3,000 to 30,000.
In this case, if the Mw is less than 1,000, the remaining film ratio of the resulting coating may be reduced, the pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. If it exceeds 000, the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.

  The alkali-soluble resin in the present invention includes, for example, an unsaturated monomer such as (meth) acrylic acid, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be produced by polymerization in the presence of a radical polymerization initiator.

The alkali-soluble resin in the present invention can be produced by radical polymerization of an unsaturated monomer as described above, followed by purification through a reprecipitation method using two or more organic solvents having different polarities. That is, after removing insoluble impurities from the solution in a good solvent after polymerization by filtration or centrifugation as necessary, a large amount (usually 5 to 10 times the volume of the polymer solution) of a precipitant (poor) Purification by pouring into the solvent) and reprecipitation of the copolymer. At that time, of the impurities remaining in the copolymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified alkali-soluble resin.
Examples of the good solvent / precipitant combination used in this reprecipitation method include diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, and methyl ethyl ketone / n-heptane. Can be mentioned.

  In addition, the alkali-soluble resin in the present invention contains each unsaturated compound as a constituent component of 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, Tetraethylthiuram disulfide, bis (pyrazol-1-ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis ( 5-methyl-pyrazol-1-ylthiocarbonyl) dis In the presence of molecular weight regulators that act as iniferters such as fido, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide In the inert solvent, the reaction temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and can be produced by living radical polymerization.

  Further, the alkali-soluble resin in the present invention is a method in which each unsaturated monomer as a constituent component is radicalized in a suitable solvent in the presence of the radical polymerization initiator and a polyvalent thiol compound that acts as a chain transfer agent. It can be produced by polymerization. Here, the polyvalent thiol compound means a compound having two or more thiol groups in one molecule, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropio). Nate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryl) Oxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5, -tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione and the like.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
In this invention, content of alkali-soluble resin is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, if the content of the alkali-soluble resin is less than 10 parts by weight, for example, the alkali developability may be reduced, or a residue or background stain may occur on the unexposed part of the substrate or the light shielding layer. When the amount exceeds 1,000 parts by weight, the pigment concentration relatively decreases, and it may be difficult to achieve the target color density as a thin film.

-(C) Polymerizable compound-
The polymerizable compound in the present invention is at least one selected from the group consisting of a dendrimer having two or more polymerizable reactive groups at its terminal and a hyperbranched polymer (hereinafter collectively referred to as “specific polymerizable compound”). ).

The specific polymerizable compound used in the present invention has a branched core part, a branched chain unit, and a terminal site, and a branched chain unit is bonded to each branched chain part of the normally branched core part. A terminal unit is bonded to a chain unit.
As the core part, an alcohol having 3 or more, particularly 4 branched structures is preferable. Moreover, as a branched chain unit, what has 3 or more branched structures is preferable, Polyamide, polyester, etc. are mentioned, However, Polyester is preferable. The terminal part should just have an ethylenic carbon-carbon double bond, and a (meth) acryloyl unit is mentioned as a suitable example.
Moreover, as a coupling | bond part of a core part and a branched chain unit, alkylene oxides, such as normal single bond; ethylene oxide, propion oxide, are mentioned, Ethylene oxide is preferable. When the bonding site is alkylene oxide, it is preferable that the oxygen terminal side of alkylene oxide is bonded to the branched chain unit.

  As the core part, pentaerythritol or mono- or polyoxyethylenated pentaerythritol is preferable. As the core part, groups represented by the following formulas (1) and (4) to (6) are preferable, and a group represented by the formula (1) is particularly preferable.

(In the formula, the arrow indicates the binding site with the branched chain unit.)

(In the formula, n represents an integer of 0 to 2, and the arrow is the same as above.)

(In the formula, the arrows are the same as above.)

(In the formula, the arrows are the same as above.)

  As the branched chain unit, a polyester unit and a polyhydroxycarboxylic acid unit are preferable, and a branched chain unit represented by the formula (2) is particularly preferable.

(In the formula, the arrow indicates the side bonded to the core part or the branched chain unit, and n represents an integer of 1 or more .)

The end piece (meth) acryloyl units of

Is preferred.

A particularly preferable example of the specific polymerizable compound is a dendrimer represented by the following formula (7).

  The specific polymerizable compound can be obtained from, for example, Osaka Organic Chemical Industry Chemical Co., Ltd., Sartomer Japan Co., etc.

In the present invention, other polymerizable compounds can be used in combination with the specific polymerizable compound. Other polymerizable compounds include, 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 both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone, and tris [2- (meth) acryloyloxyethyl] A phosphate etc. can be mentioned.

Among these other polymerizable compounds, poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, penta Erythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are preferred, especially trimethylol Propane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaa Relate, dipentaerythritol hexaacrylate, a compound represented by the following formula (8) and a compound represented by the following formula (9) have high strength of the colored layer, excellent surface smoothness of the colored layer, and unexposed. This is preferable in that ground stains, film residue, and the like hardly occur on the substrate and the light shielding layer.
The other polymerizable compounds can be used alone or in admixture of two or more.

  Content of the polymeric compound in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-400 weight part. In this case, if the content of the polymerizable compound is too low, the strength and surface smoothness of the colored layer may be reduced. On the other hand, if the content is too high, for example, the alkali developability may be reduced or the substrate on the unexposed area may be reduced. Or there is a possibility that background stains, film residue, etc. are likely to occur on the light shielding layer.

  The content of the specific polymerizable compound in the polymerizable compound is preferably 5 to 100% by weight, particularly preferably 20 to 100% by weight, from the viewpoint of obtaining the desired effect of the present invention.

In the present invention, a part of the polymerizable compound can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] ester of acid, mono (meth) acrylate of polymer having carboxy group and hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate, N- [meth) acryloyl Examples include morpholine, N-vinylpyrrolidone, and N-vinyl-ε-caprolactam. Examples of commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).

  These monofunctional monomers can be used alone or in admixture of two or more. The content ratio of the monofunctional monomer is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polymerizable compound and the monofunctional monomer. In this case, when there is too much content rate of a monofunctional monomer, there exists a possibility that the intensity | strength and surface smoothness of a colored layer to be obtained may become inadequate.

  The total content of the polymerizable compound and the monofunctional monomer 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 (B) alkali-soluble resin. . In this case, if the total amount used is too small, the strength and surface smoothness of the colored layer may be lowered. On the other hand, if the total amount is too large, for example, alkali developability may be lowered, the substrate on the unexposed area or light shielding. There is a risk that soiling, film residue, etc. are likely to occur on the layer.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is a polymer of the polymerizable compound (C) and a monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Is a compound that generates an active species capable of initiating
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. , Polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.

  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, an acetophenone compound, a biimidazole compound, a triazine compound, At least one selected from the group of O-acyloxime compounds is preferred.

  In this invention, the general content of a photoinitiator is 0.01-120 weight part normally with respect to 100 weight part of (C) polymeric compounds, Preferably it is 1-100 weight part. In this case, if the content of the photopolymerization initiator is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 120 parts by weight, the formed colored layer tends to be detached from the substrate during development.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl. ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- Examples include 1,2-diphenylethane-1-one and 1,2-octanedione.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 1,2-octanedione and the like are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, the content when an acetophenone-based compound is used as a photopolymerization initiator is usually 0.01 to 80 parts by weight, preferably 1 to 70 parts by weight, based on 100 parts by weight of the polymerizable compound (C). Parts, more preferably 1 to 60 parts by weight. In this case, if the content of the acetophenone compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement, On the other hand, when the amount exceeds 80 parts by weight, the formed colored layer tends to be detached from 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 preferable, and in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole is preferred.

These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which a colored layer pattern without an undercut is 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 content in the case of using a biimidazole compound as a photopolymerization initiator is usually 0.01 to 40 parts by weight, preferably 1 to 100 parts by weight based on 100 parts by weight of the total polymerizable compound (C). 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the content of the biimidazole compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, the developed colored layer tends to fall off from the substrate or the surface of the colored layer tends to come off during development.

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.
The hydrogen donor in the present invention is preferably a mercaptan compound or an amine compound defined below.

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 “ Amine-based hydrogen donor ").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor 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 and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A 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.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has 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 colored layer does not easily fall off from the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the 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, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 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, the content when the hydrogen donor is used in combination with the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably 1 to 40 parts by weight, based on 100 parts by weight of the total polymerizable compound (C). 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity tends to be reduced. On the other hand, if the content exceeds 40 parts by weight, the formed colored layer is detached from the substrate during development. It tends to be easy to do.

  The amine-based hydrogen donor can function as a sensitizer when used in combination with a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound. When an amine-based hydrogen donor is used as a sensitizer, the content thereof is usually 300 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of a photopolymerization initiator other than a biimidazole compound. The amount is preferably 100 parts by weight or less, but if the content is too small, it is difficult to obtain a sufficient effect. Therefore, the lower limit of the content is preferably 2 parts by weight, more preferably 5 parts by weight.

  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, the content in the case of using a triazine compound as a photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts per 100 parts by weight of the polymerizable compound (C). Part by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the triazine compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

  Examples of the O-acyloxime compound include 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6-benzoyl]. -9H-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -nonane-1 , 2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1 -[9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9H-carbazol-3-yl]- Ethan-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl- 4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned.

Among these O-acyloxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2- Dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the content when using an O-acyloxime compound as a photopolymerization initiator is preferably 0.01 to 60 parts by weight, more preferably 100 parts by weight of the polymerizable compound (C). 1 to 50 parts by weight, particularly preferably 1 to 40 parts by weight. In this case, if the content of the O-acyloxime compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 60 parts by weight, the formed colored layer tends to be detached from the substrate during development.

-Other additives-
Although the radiation sensitive composition of this invention contains the said (A)-(D) component, it can also contain another additive as needed.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anticoagulation agents such as sodium acrylate; alkali solubility improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

Solvent The radiation-sensitive composition of the present invention contains the components (A) to (D) and other additives that are optionally added. Usually, a solvent is added as a liquid composition. Prepared.
As the solvent, components (A) to (D) constituting the radiation-sensitive composition and other additive components are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it is, it can be selected and used as appropriate.

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;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
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-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
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, propylene glycol diacetate 1,3-butylene glycol diacetate, N-butyl acid, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, 3-methoxypropion Ethyl acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 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, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, 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 content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the composition is preferable from the viewpoints of applicability, storage stability, and the like of the resulting radiation-sensitive composition. Is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

Method of forming a color filter Then, using a radiation-sensitive composition of the present invention, a method for forming a color filter of the present invention.
The method for forming a color filter usually includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) A step of post-baking the developed coating film.
Hereinafter, these steps will be sequentially described.

-(1) Process-
First, on the surface of the substrate, if necessary, a light shielding layer (black matrix) is formed so as to partition a portion for forming a pixel, and, for example, a red (A) colorant is contained on the substrate. The radiation-sensitive composition of the present invention is usually applied as a liquid composition, and then pre-baked to remove the solvent by evaporation to form a coating 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 applying the liquid composition to the substrate, an appropriate coating method such as a spin coating method, a casting coating method, a roll coating method, or a coating method using a slit die coater can be employed. A coating method using 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 1.0 to 10 μm, preferably 1.0 to 6.0 μm, particularly preferably 1.0 to 4.0 μm as the film thickness after removal of the solvent.

-(2) Process-
Thereafter, at least a part of the formed coating film is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is usually 10~10,000J / m ^2. The radiation-sensitive composition of the present invention has sufficient development resistance even with an exposure dose of less than 500 J / m ² .

-(3) Process-
Then, it develops using a developing solution, Preferably an alkaline developing solution, The unexposed part of a coating film is dissolved and removed.
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 10 to 300 seconds at room temperature.

-(4) Process-
Thereafter, a post-baked coating film after development can provide a substrate on which red pixel patterns made of a cured product of the radiation-sensitive composition are arranged in a predetermined arrangement.
The post-baking conditions are preferably 180 to 230 ° C. and about 20 to 40 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Moreover, a green pixel pattern is formed on the same board | substrate by repeating the said (1)-(4) process using the green radiation sensitive composition containing a green (A) coloring agent, and also blue. (A) Using the blue radiation-sensitive composition containing the colorant, the steps (1) to (4) are repeated to form a blue pixel pattern on the same substrate, whereby red, green A pixel array in which pixel patterns of three primary colors of blue and blue are arranged in a predetermined arrangement can be formed on the substrate. However, the order of forming the pixel patterns of the respective colors can be arbitrarily selected.
A black matrix can be formed by performing the steps (1) to (4) using a green radiation-sensitive composition containing a black colorant (A).

Color Filter The color filter of the present invention has a pixel and / or a black matrix formed from the radiation-sensitive composition for forming a colored layer of the present invention.
The color filter of the present invention is extremely useful for a liquid crystal display application having a wide color reproduction region represented by TV.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element 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 with a liquid crystal layer interposed therebetween. In addition, 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 are a liquid crystal layer. It is also possible to adopt a structure that is opposed to 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 element can be obtained.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
(A) Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment Green 58 (Dainippon Ink Chemical Co., Ltd.) 9 parts by weight, C.I. I. 6 parts by weight of Pigment Yellow 150, 5 parts by weight of Disperbyk-2001 (produced by BYK) as a dispersant (solid content conversion), 80 parts by weight of 3-methoxybutyl acetate as a solvent, mixed for 12 hours by a bead mill Dispersion was performed to prepare a pigment dispersion ( A- 1).

Preparation Example 2
(A) C.I. I. 9 parts by weight of CI Pigment Green 36, C.I. I. 6 parts by weight of Pigment Yellow 150, 5 parts by weight of Disperbyk-2001 (manufactured by BYK) as a dispersant (in terms of solid content), and 3-methoxybutyl acetate as a solvent to a solid content concentration of 20% The mixture was dispersed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion ( A- 2).

Preparation Example 3
(A) C.I. I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals, trade name BK-CF), 15 parts by weight of Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) as a dispersant (solid content conversion), and propylene glycol monomethyl as a solvent A pigment dispersion ( A- 3) was prepared by mixing and dispersing ether acetate in a bead mill for 12 hours using a solid content of 20%.

Preparation Example 4
(A) 20 parts by weight of carbon black as a colorant, 4 parts by weight (converted to solids) of EFKA4046 (manufactured by Ciba Specialty Chemicals) as a dispersant, and 24% solids of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion ( A- 4) was prepared by mixing and dispersing for 12 hours using a bead mill.

(B) Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 2 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and 20 parts by weight of N-phenylmaleimide. , 55 parts by weight of benzyl methacrylate, 10 parts by weight of styrene, and 3 parts by weight of 2,4-diphenyl-4-methyl-1-pentene (manufactured by NOF Corporation, NOFMER MSD) as a molecular weight regulator, Replaced with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a resin solution (solid content concentration = 33.3% by weight). The obtained resin was Mw = 16,000 and Mn = 7,000. This resin solution is referred to as “resin solution (B-1)”.

Example 1
(A) 100 parts by weight of a pigment dispersion ( A- 1) as a colorant, (B) 5 parts by weight (in terms of solid content) of a resin solution (B-1) as an alkali-soluble resin, and (C) a dendritic compound as a polymerizable compound 15 parts by weight of biscoat # 1000 (Osaka Organic Chemical Co., Ltd.), which is a tic acrylate, and (D) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1- as a photopolymerization initiator 3 parts by weight of ON, 1 part by weight of 4,4′-bis (diethylamino) benzophenone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (S-1) having a solid concentration of 25%. The composition is shown in Table 1.
The liquid composition (S-1) was evaluated by forming a pixel pattern according to the following procedure. The evaluation results are shown in Table 2.

Pattern formation The liquid composition (S-1) was applied on a soda glass substrate on which a SiO2 film for preventing elution of sodium ions on the surface was formed using a spin coater, and then applied on a hot plate at 90 ° C. Pre-baking was performed for 5 minutes to form five coating films having a film thickness after pre-baking of 2.5 μm.
Next, after cooling these substrates to room temperature, radiation containing 365 nm, 405 nm, and 436 nm was applied to the coating film through a photomask using a high-pressure mercury lamp at 100, 200, 300, 500, 800 J / m. The exposure amount was ² . Thereafter, after developing a developing solution composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm) on these substrates, Post-baking was performed at 220 ° C. for 30 minutes to form a 200 × 200 μm dot pattern on the substrate.

Evaluation of sensitivity In the formation of the above pattern, when the film thickness ratio before and after the development of the dot pattern (film thickness after development × 100 / film thickness before development) is 95% or more, ○, before and after development When the film thickness ratio was less than 95% or chipping was found in a part of the dot pattern, Δ was evaluated, and when the pattern was completely peeled off from the substrate after development, the evaluation was ×.

Evaluation of Solvent Resistance A substrate on which a dot pattern was formed at an exposure amount of 800 J / m ² in the formation of the above pattern was immersed in N-methylpyrrolidone at 60 ° C. for 30 minutes. As a result, the case where the dot pattern was retained after immersion and the N-methylpyrrolidone after immersion was not colored at all; the dot pattern was retained after immersion, but the N-methylpyrrolidone after immersion was slightly colored The case was evaluated as Δ, and the case where the dot pattern peeled off from the substrate after immersion was observed and the N-methylpyrrolidone after immersion was colored as x.

Examples 2-14 and Comparative Examples 1-7
In Example 1, liquid compositions (S-2) to (S-21) were prepared in the same manner as in Example 1 except that the types and contents of the components were changed as shown in Table 1. The composition is shown in Table 1.
Next, various evaluations were performed in the same manner as in Example 1 except that the liquid compositions (S-2) to (S-21) were used instead of the liquid composition (S-1). The evaluation results are shown in Table 2.

In Table 1, each component is as follows.
C-1: Biscote # 1000 (dendritic acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
C-2: Biscote # 1020 (dendritic acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
C-3: CN2300 (Hyperbranch acrylate, manufactured by Sartomer Japan)
C-4: CN2302 (Hyperbranch acrylate, manufactured by Sartomer Japan)
C-5: M-402 (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei Co., Ltd.)
C-6: TO-2325 (contains 2 carboxyl groups and 10 ethylenically unsaturated groups in the molecule, manufactured by Toagosei Co., Ltd.)
D-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
D-3: 4,4′-bis (diethylamino) benzophenone

From Table 2, by introducing a dendrimer or hyperbranched polymer having an acrylate unit at the terminal site as a polymerizable compound, a radiation-sensitive composition having sufficient development resistance can be obtained even with an exposure amount of less than 500 J / m ^2. I understand. In particular, C.I. I. Pigment red 254, C.I. I. It can be seen that the solvent resistance of the radiation-sensitive composition containing CI Pigment Green 58 or carbon black is remarkably improved.

Claims (3)

(A) C.I. I. Pigment red 254, C.I. I. At least one colorant selected from the group consisting of CI Pigment Green 58 and carbon black, (B) an alkali-soluble resin, and (C) a dendrimer and a hyperbranched polymer having two or more polymerizable reactive groups at its terminals. A radiation-sensitive composition for forming a colored layer containing at least one polymerizable compound selected from the group and (D) a photopolymerization initiator, wherein the dendrimer and the hyperbranched polymer have a branched chain. Part, a branched chain unit bonded to the branched chain part of the core part, and a terminal site bonded to the branched chain unit, wherein the core part has the formula (1)

(In the formula, the arrow indicates the binding site with the branched chain unit.)
Wherein the branched chain unit is represented by the formula (2)

(In the formula, the arrow indicates the side bonded to the core part or the branched chain unit, and n represents an integer of 1 or more.)
A radiation-sensitive composition for forming a colored layer, wherein the terminal site is a (meth) acryloyl unit. A color filter comprising a colored layer formed using the radiation-sensitive composition according to claim 1 . A color liquid crystal display device comprising the color filter according to claim 2 .