JP2009229979A - Radiation-sensitive composition for colored layer formation, color filter, and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition for colored layer formation by which a pixel with excellent transparency and high brightness can be formed. <P>SOLUTION: The radiation-sensitive composition for colored layer formation contains (A) a colorant, (B) a polymer containing a group expressed by a formula (1) represented by a decahydronaphthyl group, (C) a multifunctional monomer, and (D) photopolymerization initiator. In the formula (1), R is halogen atom, hydroxyl group, or monovelent organic group; n is integer of 0-9; and * is bond. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of red, green, and blue colors by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it (see, for example, Patent Document 1 and Patent Document 2). Are known.

  By the way, in order for the liquid crystal display element to exhibit excellent display performance, the color space expression ability of the pixel is important. Each color pixel of red, green, and blue is toned so that the color reproduction region determined by the chromaticity coordinates (x, y) in the XYZ color system can be sufficiently widened, and the luminance represented by the stimulus value Y is sufficiently high. It is required to have excellent transparency and color purity. However, in the production process of the color filter, there is a problem that transparency and color characteristics of the colored layer are impaired by the resin component and the photopolymerization initiator contained in the colored radiation-sensitive composition. Specifically, the color filter is manufactured through a heating process involving high temperature such as post-baking or polyimide alignment film formation. In such a heating process, the resin component or the photopolymerization initiator is yellowed, or Since the resin component and the photopolymerization initiator are originally slightly colored in yellow, there is a problem that the color characteristics of the colored layer deteriorate. Among each color, in particular, when the blue pixel is yellowish, the transparency, the color characteristics are deteriorated, and the luminance is most deteriorated. Therefore, the resin component and the photopolymerization initiator in the colored radiation-sensitive composition for forming the blue pixel are used. The choice is particularly important.

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

  This invention is made | formed based on the above situations, The subject is providing the novel radiation sensitive composition for colored layer formation which can form a pixel excellent in transparency and high brightness | luminance. It is in.

  As a result of intensive studies, the present inventors have found that the above-described problems can be solved by incorporating a specific polymer in the radiation-sensitive composition for forming a colored layer, and have completed the present invention.

That is, the present invention firstly
(A) a colorant, (B) a polymer having a group represented by the following formula (1) (hereinafter sometimes referred to as “(B) polymer”), (C) a polyfunctional monomer, And (D) a radiation sensitive composition for forming a colored layer, comprising a photopolymerization initiator.
The “radiation” as used in the present invention means a substance containing visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like.

(In Formula (1), R represents a halogen atom, a hydroxyl group or a monovalent organic group, n represents an integer of 0 to 9, and “*” represents a bond.)

The present invention secondly,
A color filter provided with a colored layer formed using the radiation-sensitive composition for forming the colored layer.
Third, the present invention
A color liquid crystal display device comprising the color filter;

Hereinafter, the present invention will be described in detail.
Colored layer forming radiation-sensitive composition of the colored layer forming radiation-sensitive composition <br/> present invention the term "colored layer" in (hereinafter referred to simply as "radiation-sensitive composition".) It means a layer composed of pixels and / or a black matrix used for a color filter.
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 180, 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, various commercially available polymers or oligomers for dispersing pigments, and the like. 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.
Moreover, the radiation sensitive composition of this invention is especially useful at the point which improves the brightness | luminance of the colored layer formed using the radiation sensitive composition containing a blue pigment as (A) colorant.
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).

  In this invention, it is preferable that content of (A) coloring agent is 5-70 mass% in the total solid content from the point which forms the colored layer excellent in transparency and color purity, and is 5-60 mass%. More preferably it is. 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, an alkyl ammonium salt or a phosphate ester salt of a high molecular copolymer, 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 polymers 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, polyurethanes, 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)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and cationic comb-type graft polymer Solsperse 24000, Solsperse 37500 (manufactured by Lubrizol Corporation), Addisper PB821, Addispar PB822, Addisper PB880 (Ajinomoto Fine Techno Co., Ltd.) And the like can be given.

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) polymer-
In the present invention, the polymer (B) acts as a binder for the colorant (A), and in the case of constituting a radiation-sensitive composition capable of alkali development, a development treatment for forming a colored layer. There is no particular limitation as long as it is a component that expresses solubility in an alkaline developer used in the process and is a polymer having a group represented by the above formula (1).

  As a halogen atom of R in the said Formula (1), a fluorine atom, a chlorine atom, etc. can be mentioned, for example. Moreover, as a monovalent organic group of R in the said Formula (1), an ethyl group, i-propyl group, a carboxyl group etc. can be mentioned, for example. In the above formula (1), n is preferably 0.

As the polymer (B), for example, (b1) an ethylenically unsaturated monomer having a group represented by the above formula (1) (hereinafter sometimes referred to as “compound (b1)”) is contained. And a polymer of a polymerizable unsaturated monomer (hereinafter sometimes referred to as “polymer (B1)”).
Examples of the compound (b1) include an ethylenically unsaturated monomer having a group represented by the following formula (2), a compound represented by the following formula (3), and the like.

(In Formula (2), R and n have the same meanings as R and n in Formula (1), respectively, and “*” represents a bond.)

(In Formula (3), R ¹ represents a single bond, a methylene group or a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, R ² represents an ethylene group or a propylene group, and m is an integer of 0 to 10) R and n have the same meanings as R and n in the above formula (1), respectively.
In the above formula (2), n is preferably 0. Examples of the ethylenically unsaturated monomer having a group represented by the above formula (2) include an ethylenically unsaturated monomer having a compound represented by the following formula (4) and a carboxyl group or an acid anhydride group. An esterified product with a monomer can be mentioned, and the esterified product can be synthesized by a known method.

(In Formula (4), R and n are synonymous with R and n in Formula (1), respectively.)
The compound represented by the above formula (4) is preferably a compound in which n is 0. For example, decahydro-2-naphthol is commercially available from Sugai Chemical Industry Co., Ltd.
Examples of the ethylenically unsaturated monomer having a carboxyl group or an acid anhydride group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; Unsaturated dicarboxylic acids such as acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like; succinic acid mono [2- (meth) acryloyloxyethyl] Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as phthalic acid mono [2- (meth) acryloyloxyethyl]; ω-carboxypolycaprolactone mono (meth) acrylate, etc. Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends.

In the above formula (3), R ¹ is preferably a single bond or a methylene group, m is preferably 0 to 8, and n is preferably 0.

Specific examples of the compound (b1) include esterified products of decahydro-1-naphthol and (meth) acrylic acid (decahydro-1-naphthyl (meth) acrylate), decahydro-2-naphthol and (meta ) Esterified product with acrylic acid (decahydro-2-naphthyl (meth) acrylate), monoester product of decahydro-1-naphthol and maleic acid, diesterified product of decahydro-1-naphthol and maleic acid, decahydro- 2-esterified product of 2-naphthol and maleic acid, diesterified product of decahydro-2-naphthol and maleic acid, esterified product of decahydro-1-naphthol and succinic acid mono [2- (meth) acryloyloxyethyl], Decahydro-2-naphthol and succinic acid mono [2- (meth) acrylate Esterified product with leuoxyethyl], esterified product of decahydro-1-naphthol and ω-carboxypolycaprolactone mono (meth) acrylate, decahydro-2-naphthol and ω-carboxypolycaprolactone mono (meth) acrylate Esterified product, decahydro-1-naphthyl vinyl ether, decahydro-2-naphthyl vinyl ether, decahydro-1-naphthyl allyl ether, decahydro-2-naphthyl allyl ether, decahydro-1-naphthyl (vinyloxyethyl) ether, Examples include decahydro-2-naphthyl (vinyloxyethyl) ether. Of these, decahydro-2-naphthyl (meth) acrylate is commercially available from Sugai Chemical Industry Co., Ltd.
In the present invention, the compound (b1) is preferably an ethylenically unsaturated monomer having a group represented by the above formula (2) from the viewpoint of transparency and heat resistance, and decahydro-2-naphthyl (meth). Acrylate is particularly preferred.
A compound (b1) can be used individually or in mixture of 2 or more types.

In the polymer (B1), it is preferable to copolymerize a polymerizable unsaturated monomer other than the compound (b1) (hereinafter sometimes referred to as “compound (b2)”) together with the compound (b1).

As the compound (b2), for example,
An ethylenically unsaturated monomer having a carboxyl group or an acid anhydride group;
o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Unsaturated phenols such as
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols;
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-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl 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;
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, polysiloxane and the like.

In the present invention, the compound (b2) includes an ethylenically unsaturated monomer having a carboxyl group, an unsaturated phenol, an N-substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and a polymer molecular chain. It is preferable to contain at least one selected from the group consisting of macromonomers having a mono (meth) acryloyl group at the end, in particular (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Allyl (meth) acrylate, benzyl (meta It is preferable to contain at least one selected from the group consisting of acrylate), cyclohexyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, polystyrene macromonomer, and polymethylmethacrylate macromonomer.
A compound (b2) can be used individually or in mixture of 2 or more types.

In the present invention, the polymer (B1) can be used alone or in admixture of two or more. For example, JP-A-7-140654, JP-A-10-300922 and JP-A-11- 174224, JP-A-11-258415, JP-A-2000-56118, and the like can also be used by mixing with other polymers typified by binder polymers and alkali-soluble resins.
When the polymer (B1) is used alone, the content of the repeating unit derived from the compound (b1) in the polymer (B1) is preferably 1 to 90% by weight, more preferably 5 to 70% by weight. Even when the polymer (B1) is mixed with another polymer and used, the content of the repeating unit derived from the compound (b1) is adjusted to the above range with respect to the whole polymer. Is preferred. In addition, in order to obtain a radiation-sensitive composition capable of alkali development, when the polymer (B1) is used alone, a repeating unit derived from an ethylenically unsaturated monomer having a carboxyl group in the polymer (B1). Is preferably 5 to 50% by weight, and more preferably 10 to 40% by weight. Even when the polymer (B1) is used by mixing with another polymer, the content of the repeating unit derived from the ethylenically unsaturated monomer having a carboxyl group is the above-mentioned content of the whole polymer. It is preferable to adjust to the range.

In this case, if the content of the repeating unit derived from the compound (b1) is less than 1% by weight, the desired effect may not be obtained, while if it exceeds 90% by weight, the alkali of the resulting radiation-sensitive composition may be obtained. There is a tendency that the solubility in a developer is lowered. In addition, when the content of the repeating unit derived from the ethylenically unsaturated monomer having a carboxyl group is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, If it exceeds 50% by weight, the solubility in an alkaline developer tends to be excessive, and when developing with an alkaline developer, the pixel tends to drop off from the substrate and the pixel surface becomes rough.

  In the present invention, for example, a polymer (B1) obtained by copolymerizing a polymerizable unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, and the like such as 2- (meth) acryloyloxyethyl isocyanate By reacting the unsaturated isocyanate compound, a polymerizable unsaturated bond can be introduced into the side chain of the copolymer (B).

  The polymer (B1) is prepared by, for example, treating each polymerizable unsaturated monomer with 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) in a suitable solvent. ), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like in the presence of a radical polymerization initiator.

The polymer (B1) can be produced by radical polymerization of the polymerizable unsaturated monomer as described above and then purifying 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) The polymer (B1) is reprecipitated by pouring into the solvent) and purification. At that time, out of the impurities remaining in the copolymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified polymer (B1).
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 polymer (B1) contains each polymerizable unsaturated monomer, the radical polymerization initiator, 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) disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide Iniferter etc. The presence of molecular weight control agents which act as an inert solvent, the reaction temperature, usually, 0 to 150 ° C., preferably as 50 to 120 ° C., can be produced by living radical polymerization.

Furthermore, the polymer (B1) is obtained by radical polymerizing each polymerizable unsaturated monomer in an appropriate solvent in the presence of the above radical polymerization initiator and a polyvalent thiol compound that acts as a chain transfer agent. Can be manufactured. 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 the present invention, the weight average molecular weight in terms of polystyrene (hereinafter sometimes referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer (B) in the present invention is preferably from 1,000 to 1,000. It is 45,000, More preferably, it is 3,000-30,000.
The number average molecular weight (hereinafter referred to as “Mn”) in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the polymer (B) in the present invention is preferably 1,000 to 45. 3,000, more preferably 3,000 to 30,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the polymer (B) in the present invention is preferably 1 to 5, and more preferably 1 to 4.
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.

  In the present invention, the content of the polymer (B) is usually 10 to 1,000 parts by weight, preferably 20 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. In this case, if the content of the polymer (B) is less than 10 parts by weight, for example, the alkali developability may decrease, or a residue or background stain may occur on the unexposed part of the substrate or the light shielding layer. On the other hand, when the amount exceeds 1,000 parts by weight, the pigment concentration is relatively lowered, so that it may be difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As such a polyfunctional 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 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 end hydroxyl polymers such as both end hydroxypoly-1,3-butadiene, both end hydroxypolyisoprene, both end hydroxypolycaprolactone;
Tris [2- (meth) acryloyloxyethyl] phosphate,
Isocyanuric acid ethylene oxide modified triacrylate;
Examples thereof include poly (meth) acrylate having a urethane structure.

Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols, their dicarboxylic acid-modified products, and poly (meth) acrylates having a urethane structure are preferred. Examples of poly (meth) acrylates of trihydric or higher polyhydric alcohols and their modified dicarboxylic acids include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate. , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid, pentaerythritol trimethacrylate and succinic acid Monoesterified product with dipentaerythritol Monoesterified products of acrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid are preferred, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Monoesterified product of hexaacrylate, pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of colored layer, excellent surface smoothness of 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 said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The content of the polyfunctional 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 polymer (B). In this case, when the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, when the amount exceeds 500 parts by weight, for example, alkali developability is reduced. In addition, background stains, film residue, etc. tend to occur on the unexposed portion of the 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 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 a polymer having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; N-vinylsuccinimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinyl Indole, N-vinylindoline, N-vinylbenzimidazole, N-vinylcal N-vinyl nitrogen-containing heterocyclic compounds such as azole, N-vinyl piperidine, N-vinyl piperazine, N-vinyl morpholine, N-vinyl phenoxazine; in addition to N- (meth) acryloyl morpholine, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like can be mentioned.
These monofunctional monomers can be used alone or in admixture of two or more.

  The content ratio of the monofunctional monomer in the present invention is preferably 90% by weight or less, more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the pixel tend to be lowered.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer used in some cases upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species capable of initiating polymerization of the body.
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, and the like.

  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 the present invention, the general content of the photopolymerization initiator is usually 0.01 to 120 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the (C) polyfunctional monomer. is there. 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 in the case of using an acetophenone-based compound as a photopolymerization initiator is usually 0.01 to 80 parts by weight, preferably 1 with respect to 100 parts by weight of the (C) polyfunctional monomer. -70 weight part, More preferably, it is 1-60 weight part. 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) -4,4 ', 5,5'-tetrafe 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 100 parts by weight of the total of (C) polyfunctional monomers. Is 1-30 parts by weight, more preferably 1-20 parts by weight. In this case, if the content of the biimidazole 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 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 one 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.
Further, when the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups are substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. 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.
Further, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a 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.
Of these amine-based 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 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 100 parts by weight of the total of (C) polyfunctional monomers. Is 1 to 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 cistyryl) -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 when using a triazine compound as a photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably 100 parts by weight of (C) polyfunctional monomer. 1 to 30 parts 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 an O-acyloxime compound is used as the photopolymerization initiator is preferably 0.01 to 60 parts by weight with respect to 100 parts by weight of the (C) polyfunctional monomer, More preferably, it is 1-50 weight part, Most preferably, it is 1-40 weight part. 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.

-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 for forming a colored layer according to the present invention contains the components (A) to (D) as essential components, and optionally contains the additive component. Prepared as a composition.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl 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;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-acetate -Amyl, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2 -Other esters such as ethyl oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability and the like, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, butyric acid - propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is usually An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.

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 blue (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. In addition, according to the radiation sensitive composition of this invention, a pixel and a black matrix can be formed even if a prebaking process is omitted.
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.

-(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.
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-
Then, the post-baked coating film after development can provide a substrate on which blue 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 red pixel pattern is formed on the same board | substrate by repeating the said (1)-(4) process using the red radiation sensitive composition containing a red (A) coloring agent, and also green. (A) Using the green radiation-sensitive composition containing the colorant, the steps (1) to (4) are repeated to form a green 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 pixels and / or a black matrix formed as described above from the radiation-sensitive composition of the present invention.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
Further, as one form of the color liquid crystal display element of the present invention, a pixel and / or a black matrix is formed as described above on the thin film transistor substrate array using the radiation-sensitive composition for forming a colored layer of the present invention. By doing so, a color liquid crystal display element having excellent transparency and high luminance can be produced.

According to the radiation-sensitive composition of the present invention, a pixel having excellent transparency and high luminance can be formed.
Therefore, the radiation-sensitive composition of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display elements in the electronic industry.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. 15 parts by weight of Pigment Blue 15: 6, 5 parts by weight of Disperbyk-2000 (produced by BYK) as a dispersant (in terms of solid content), and a solid content concentration of 20% of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (M-1) was prepared by mixing and dispersing with a bead mill for 12 hours.

Preparation Example 2
(A) C.I. I. Pigment Blue 15: 6, 12 parts by weight, C.I. I. 3 parts by weight of Pigment Violet 23, 5 parts by weight of Disperbyk-2000 (manufactured by BYK Co., Ltd.) as a dispersant (in terms of solid content), and propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 20% Then, the pigment dispersion (M-2) was prepared by mixing and dispersing with a bead mill for 12 hours.

(B) Synthesis of polymer Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 43 parts by weight of decahydro-2-naphthyl methacrylate and methacrylic acid. 15 parts by weight, 15 parts by weight of 2-hydroxyethyl methacrylate, 15 parts by weight of N-phenylmaleimide, 12 parts by weight of styrene, and 2,4-diphenyl-4-methyl-1-pentene (manufactured by NOF Corporation) (Product name: NOFMER MSD) 5 parts by weight were charged, and the atmosphere was 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 polymer solution (solid content concentration = 33.3% by weight). The obtained polymer was Mw = 12,000 and Mn = 7,000. This polymer solution is referred to as “polymer solution (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 30 parts by weight of decahydro-2-naphthyl methacrylate and methacrylic acid. 15 parts by weight, 15 parts by weight of 2-hydroxyethyl methacrylate, 15 parts by weight of N-phenylmaleimide, 12 parts by weight of styrene, 8 parts by weight of benzyl methacrylate, 5 parts by weight of n-butyl methacrylate and 2,4-diphenyl- as a molecular weight regulator 5 parts by weight of 4-methyl-1-pentene (trade name: NOFMER MSD, manufactured by NOF Corporation) was charged, and the atmosphere was 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 polymer solution (solid content concentration = 33.3% by weight). The obtained polymer was Mw = 12,000 and Mn = 7,000. This polymer solution is referred to as “polymer solution (B-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 3 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 15 parts by weight of 2-hydroxyethyl methacrylate. Parts, N-phenylmaleimide 15 parts by weight, styrene 12 parts by weight, benzyl methacrylate 23 parts by weight, n-butyl methacrylate 20 parts by weight and 2,4-diphenyl-4-methyl-1-pentene (Nippon Oils and Fats) Co., Ltd. product name: NOFMER MSD) was charged with 5 parts by weight, and the atmosphere was 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 polymer solution (solid content concentration = 33.3% by weight). The obtained polymer was Mw = 12,000 and Mn = 7,000. This polymer solution is referred to as “polymer solution (B-3)”.

Example 1
(A) 100 parts by weight of a pigment dispersion (M-1) as a colorant, (B) 20 parts by weight (in terms of solid content) of a polymer solution (B-1) as a polymer, (C) a polyfunctional monomer As a commercial product containing a polyfunctional acrylate having a urethane structure (trade name: KAYARAD DPHA-40H, manufactured by Nippon Kayaku Co., Ltd.), (D) 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals), 2 parts by weight of 4,4′-bis (diethylamino) benzophenone, and solvent As a mixture, propylene glycol monomethyl ether acetate was mixed to prepare a liquid composition (R-1) having a solid concentration of 25%.
The liquid composition (R-1) was evaluated by forming a pixel pattern according to the following procedure. The evaluation results are shown in Table 1.

Forming a pattern After applying 5 liquid compositions (R-1) on a soda glass substrate on which a SiO2 film for preventing elution of sodium ions is formed on the surface using a spin coater with variable number of rotations. Then, pre-baking was performed for 4 minutes on a hot plate at 90 ° C. to form five coating films having different film thicknesses.
Next, after cooling these substrates to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 1,000 J / m ² through a photomask using a high-pressure mercury lamp. did. 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 Chromaticity For the obtained blue dot pattern, using a color analyzer (MCPD2000, manufactured by Otsuka Electronics Co., Ltd.), C light source, chromaticity coordinate value (x, y) in the CIE color system in a 2 degree visual field, and The stimulus value (Y) was measured. From the measurement results, a chromaticity coordinate value x and a stimulus value (Y) at which the chromaticity coordinate value y is 0.179 were obtained. The evaluation results are shown in Table 1. It shows that luminance (transparency) is so high that the value of a stimulus value (Y) is large.

Examples 2-4 and Comparative Examples 1-2
In Example 1, liquid compositions (R-2) to (R-6) were prepared in the same manner as in Example 1 except that the types of each component were changed as shown in Table 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (R-2) to (R-6) were used in place of the liquid composition (R-1). The evaluation results are shown in Table 1. When the pigment dispersion (M-1) was used, the chromaticity coordinate value x and the stimulation value (Y) at which the chromaticity coordinate value y was 0.179 were used for the pigment dispersion (M-2). In this case, the chromaticity coordinate value x and the stimulus value (Y) at which the chromaticity coordinate value y is 0.080 were obtained and evaluated.

  As can be seen from Table 1, the inclusion of a copolymer of decahydro-2-naphthyl methacrylate improves the stimulation value (Y), which is an index of brightness, by 0.3 to 1.1 points. Recognize.

Claims (5)

It contains (A) a colorant, (B) a polymer having a group represented by the following formula (1), (C) a polyfunctional monomer, and (D) a photopolymerization initiator. A radiation-sensitive composition for forming a colored layer.

(In Formula (1), R represents a halogen atom, a hydroxyl group or a monovalent organic group, n represents an integer of 0 to 9, and “*” represents a bond.) The radiation sensitive composition for colored layer formation according to claim 1, wherein the polymer (B) has a repeating unit derived from an ethylenically unsaturated monomer having a group represented by the following formula (2).

(In Formula (2), R and n have the same meanings as R and n in Formula (1), respectively, and “*” represents a bond.) (A) The radiation sensitive composition for colored layer formation of Claim 1 or 2 containing a blue pigment as a coloring agent. The color filter provided with the colored layer formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-3. A color liquid crystal display device comprising the color filter according to claim 4.