JP7059620B2 - Photosensitive coloring compositions for color filters and color filters - Google Patents

Description

The present invention relates to a coloring composition for a color filter used for manufacturing a color filter used for manufacturing a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed by using the coloring composition. Is.

In recent years, there has been an increasing demand for precise substrate design in color filters, and along with this, there is a strong demand for high resolution of photosensitive coloring compositions. The resolution of the photosensitive coloring composition is generally adjusted by the type and amount of the photopolymerization initiator and the monomer, but in the conventional photosensitive coloring composition, the surface of the coating film on a thick film is used. It is difficult to achieve both high smoothness and high linearity of the patterned coating. In addition to this, it is also required to improve the stability of the coating film in commercialization, and the coating film is required to have high heat resistance. That is, the achievement of a photosensitive coloring composition that satisfies all of the high surface smoothness, high linearity, and high heat resistance of the resist coating film is an issue. It has been reported that a polyfunctional urethane acrylate having a triazine skeleton is effective only for the smoothness of the coating film surface (see Patent Document 1), but it is difficult to satisfy all the above-mentioned problems.

Japanese Unexamined Patent Publication No. 2012-098345

An object of the present invention is to provide a photosensitive coloring composition for a color filter, which enables all of high surface smoothness, high linearity, and high heat resistance of a resist coating film, and a color filter using the same.

As a result of intensive studies to solve the above problems, the present inventors have added the following copolymers (a) and (b) to the photosensitive coloring composition, and then (c) to (d). ), And a polyfunctional urethane acrylate (C1) containing 8 or more (meth) acryloyl groups in one molecule and having a triazine skeleton, and the content of (C1). The present invention has been found to be able to achieve all of high surface smoothness, high linearity, and high heat resistance of the resist coating film when the amount of the photopolymerizable monomer (C) is 40 to 100% by mass with respect to the total amount. It was made.
(A): Cyclic ether skeleton having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond (b): A single unsaturated bond different from (a) and having an unsaturated bond copolymerizable with (a). Quantum (c): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): Polybasic acid anhydrides

<1> A photosensitive coloring composition for a color filter containing a colorant (A), a resin (B), a photopolymerizable monomer (C) and a photopolymerization initiator (D).
The resin (B) contains the following copolymer (a) and (b), which is reacted with (c) and then reacted with (d), and contains the resin (B1).
(A): Cyclic ether skeleton having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond (b): It has an unsaturated bond that can be copolymerized with (a) and is different from (a). Quantum (c): At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (d): Polybasic acid anhydride Photopolymerizable monomer (C) is contained in one molecule. It contains 8 or more (meth) acryloyl groups and contains a polyfunctional urethane acrylate (C1) having a triazine skeleton.
A photosensitive coloring composition for a color filter in which the content of the polyfunctional urethane acrylate (C1) is 40 to 100% by mass with respect to the total amount of the photopolymerizable monomer (C).

<2> The photosensitive coloring composition for a color filter, wherein the photopolymerization initiator (D) contains an oxime ester-based photopolymerization initiator.

<3> The photosensitive coloring composition for a color filter, which further contains an antioxidant (E).

<4> A color filter comprising a filter segment formed from the photosensitive coloring composition for a color filter on a substrate.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive coloring composition for a color filter capable of forming a coating film exhibiting high surface smoothness, high linearity and high heat resistance of a resist coating film. Further, it is possible to provide a high quality color filter having the above performance.

The photosensitive coloring composition for a color filter of the present invention contains a colorant (A), a resin (B), a photopolymerizable monomer (C) and a photopolymerization initiator (D), and the resin (B) contains. The following copolymer of (a) and (b) contains the resin (B1) obtained by reacting (c) and then (d), and the photopolymerizable monomer (C) is contained in one molecule (C). Meta) Contains a polyfunctional urethane acrylate (C1) containing 8 or more acryloyl groups and having a triazine skeleton, and the content of the polyfunctional urethane acrylate (C1) is the total amount of the photopolymerizable monomer (C). On the other hand, it is characterized in that it is 40 to 100% by mass.
(A): Cyclic ether skeleton having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond (b): It has an unsaturated bond that can be copolymerized with (a) and is different from (a). Quantum (c): At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (d): Polybasic acid anhydride Photopolymerizable monomer (C) is contained in one molecule. It contains 8 or more (meth) acryloyl groups and contains a polyfunctional urethane acrylate (C1) having a triazine skeleton.
A photosensitive coloring composition for a color filter in which the content of the polyfunctional urethane acrylate (C1) is 40 to 100% by mass with respect to the total amount of the photopolymerizable monomer (C).

Hereinafter, the present invention will be described in detail.
In the present application, when "(meth) acrylate", "(meth) acrylic acid", or "(meth) acrylamide" is described, "acrylate and / or methacrylate", respectively, unless otherwise specified. It shall represent "acrylic acid and / or methacrylic acid" or "acrylamide and / or methacrylamide".

<Photosensitive coloring composition for color filters>
<Colorant (A)>
The photosensitive coloring composition for a color filter of the present invention contains a colorant (A). As the colorant (A), an organic or inorganic pigment can be used alone or in combination of two or more. Among the pigments, pigments having high color development and high heat resistance are preferable, and organic pigments are usually used. Hereinafter, specific examples of organic pigments that can be used in the photosensitive coloring composition of the present invention are shown by color index numbers. Further, as the colorant (A), a dye can be contained within a range that does not reduce the heat resistance.

《Pigment》
Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254. , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Among these, from the viewpoint of lightness and coloring power, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based dyes can be mentioned. Specifically, C.I. I. Pigment Red 176, 177, 179, 254, 242, a naphthol azo pigment represented by the following general formula is preferable.

[In the formula, A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or COOR ⁸ . ^R2 to R6 are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, alkyl group having 1 to ⁴ carbon atoms, -OR ⁹ , -COOR ¹⁰ , -CONHR ¹¹ , -Represents NHCOR ¹² or SO ₂ NHR ¹³ . R ⁷ to R ¹³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, more preferably C.I. I. Pigment Blue 15: 6. Further, the aluminum phthalocyanine pigments and the like described in JP-A-2004-333817, Japanese Patent No. 4893859 and the like can also be used, and the present invention is not particularly limited thereto.

Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 Can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment green 7, 36 or 58. Further, the zinc phthalocyanine pigments and the like described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-070342 and the like can also be used, and the present invention is not particularly limited thereto.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and the like can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment Yellow 138, 139, 150, 185, a quinophthalone compound represented by the following general formula.

[In the formula, X1 to X13 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryl which may have a substituent. Group, -SO ₃ H group, -COOH group, -SO ₃ H group or -COOH group metal salt, -SO ₃ H group or -COOH group alkylammonium salt, phthalimide methyl group which may have a substituent. , Or a sulfamoyl group which may have a substituent. Adjacent groups of X1 to X4 and / or X10 to X13 together form an aromatic ring that may have a substituent. ]

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a petit group, an isoptyl group, a tert-ptyl group, a neopentyl group, an n-hexyl group and an n-octyl group. In addition to linear or branched alkyl groups such as groups, stearyl groups and 2-ethylhexyl groups, trichloromethyl groups, trifluoromethyl groups, 2,2,2-trifluoroethyl groups, 2,2-dibromoethyl groups, 2,2,3,3-Tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pendyl group, 4-methylpentyl group, 4-tert-ptylbenzyl group, 4-methoxy Examples thereof include an alkyl group having a substituent such as a penzyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group.

Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-ptyloxy group, a neopentyloxy group, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-Trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples thereof include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

The aryl group which may have a substituent includes an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and p-. Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-Trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having substituents can be mentioned.

Examples of the acidic group include -SO _3H and -COOH, and the monovalent to trivalent metal salts of these acidic groups include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt and aluminum salt. And so on. Examples of the alkylammonium salt of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and quaternary alkyls such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. Ammonium salt can be mentioned.

"Substituents" in the phthalimidemethyl group (C ₆ H ₄ (CO) ₂ N-CH _2- ) which may have a substituent and the sulfamoyl group (H ₂ NSO _2- ) which may have a substituent. Examples thereof include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent and the like.

Adjacent groups of X1 to X4 and / or X10 to X13 in the formula may be integrated to form an aromatic ring having a substituent.
Examples of the aromatic ring here include a hydrocarbon aromatic ring and a heteroaromatic ring, examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and examples of the heteroaromatic ring include pyridine. Examples thereof include a ring, a pyrazine ring, a pyrrol ring, a quinoline ring, a quinoxalin ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 64, 71, or 73 and the like. Above all, from the viewpoint of brightness and coloring power, C.I. I. Pigment Oranges 38, 43 and 64 are preferred.

Examples of the black photosensitive coloring composition for forming a black matrix include carbon black, aniline black, anthraquinone-based black pigment, and perylene-based black pigment, specifically, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. A mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black photosensitive coloring composition. As the black pigment, carbon black is preferable from the viewpoint of price and light-shielding property, and the carbon black may be surface-treated with a resin or the like. Further, in order to adjust the color tone, a blue pigment or a purple pigment can be used in combination with the black photosensitive coloring composition.

Inorganic pigments include barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, dark blue, chromium oxide green, cobalt green, amber, and titanium black. , Synthetic iron black, titanium oxide, metal oxide powder such as iron tetroxide, metal sulfide powder, metal powder and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

《Pigment miniaturization》
In the present invention, the pigment can be refined by performing a salt milling treatment. The primary particle size of the pigment is preferably 20 nm or more because it is well dispersed in the colorant carrier. Further, since it is possible to form a filter segment having a high contrast ratio, it is preferably 100 nm or less. A particularly preferable range is the range of 25 to 85 nm. The primary particle size of the pigment was determined by a method of directly measuring the size of the primary particle from an electron micrograph of the pigment by TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube having a obtained particle size, and the volume average particle size is defined as the average primary particle size.

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a trimix, a ball mill, an attritor, or a sand mill. This is a treatment in which the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the pigment.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins and the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

"dye"
The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce the heat resistance, and two or more kinds may be used in combination.
The dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, and thiazines. Dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, anthancelon dyes, isoindrinone Examples thereof include, but are not limited to, dyes, isoindrin dyes, indanthron dyes, coumarin dyes, quinacridone dyes, pyranthron dyes, flavanthron dyes, and perinone dyes.

Of the organic dyes mentioned above, acid dyes can have high heat resistance, light resistance, and solvent resistance by forming chlorides and sulfonamides as quaternary ammonium salts.

(Salt-forming compound consisting of acid dye and quaternary ammonium salt compound)
When the organic dye used in the present invention is an acid dye, it is preferably used as a salt-forming compound composed of an acid dye and a quaternary ammonium salt compound.

[Quaternary ammonium salt compound]
A quaternary ammonium salt compound as a counter component of an acid dye will be described. The quaternary ammonium salt compound has an amino group and thus serves as a counter for acid dyes.

The preferred form of the quaternary ammonium salt compound, which is a counter component of the salt-forming compound, is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. It is a thing. That is, it is necessary that the dye component does not hinder the color development and does not cause a color change.

The molecular weight of the counter portion, which is a cationic component of the quaternary ammonium salt compound, is preferably in the range of 190 to 900. Here, the cation portion corresponds to the portion of (NR ₁ R ₂ R ₃ R ₄ ) ⁺ in the following general formula (3). If the molecular weight is smaller than 190, the light resistance and heat resistance are lowered, and the solubility in a solvent is further lowered. Further, when the molecular weight becomes larger than 900, the ratio of the color-developing component in the molecule decreases, the color-developing property decreases, and the brightness also decreases. More preferably, the molecular weight of the counter portion is in the range of 240 to 850. Particularly preferred is the molecular weight of the counter portion in the range of 350 to 800. Here, the molecular weight was calculated based on the structural formula, and the atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

Further, as the quaternary ammonium salt compound, a compound represented by the following general formula (30) is used.

General formula (30)

(In the general formula (30), R ₁ to R ₄ independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least two or more of R ₁ , R ₂ , R ₃ and R ₄ are present. The number of C is 5 to 20. Y ^- represents an inorganic or organic anion.)

By setting the number of at least two or more Cs of R ₁ to R ₄ to 5 to 20, the solubility in a solvent becomes good. When the number of C is less than 5, the number of alkyl groups is 3 or more, the solubility in a solvent is deteriorated, and foreign matter in the coating film is likely to be generated. Further, if an alkyl group having an C number of more than 20 is present, the color-developing property of the salt-forming compound is impaired.

Specifically, tetramethylammonium chloride (the cation portion has a molecular weight of 74), tetraethylammonium chloride (the cation portion has a molecular weight of 122), monostearyltrimethylammonium chloride (the cation portion has a molecular weight of 312), and distearyldimethylammonium chloride (the cation portion has a molecular weight of 312). The cation portion has a molecular weight of 550), tristearyl monomethylammonium chloride (cation portion has a molecular weight of 788), cetyltrimethylammonium chloride (cation portion has a molecular weight of 284), trioctylmethylammonium chloride (cation portion has a molecular weight of 368), and dioctyl. Dimethylammonium chloride (cation part has a molecular weight of 270), monolauryltrimethylammonium chloride (cation part has a molecular weight of 228), dilauryldimethylammonium chloride (cation part has a molecular weight of 382), and trilaurylmethylammonium chloride (cation part has a molecular weight of 382). 536), triamilbenzylammonium chloride (cation part molecular weight 318), trihexylbenzylammonium chloride (cation part molecular weight 360), trioctylbenzylammonium chloride (cation part molecular weight 444), trilaurylbenzylammonium Chloride (cationic moiety molecular weight 612), benzyldimethylstearylammonium chloride (cationic moiety molecular weight 388), and benzyldimethyloctylammonium chloride (cationic moiety molecular weight 248), dialkyl (alkyl C14-C18) dimethylammonium chloride It is preferable to use (hardened beef fat) (the molecular weight of the cation portion is 438 to 550) or the like.

The component of Y ⁻ constituting the anion may be an inorganic or organic anion, but is preferably a halogen and is usually chlorine.

Specific products of the quaternary ammonium salt compound include Kao Corporation's Coatamine 24P, Coatamine 86P Conch, Coatamine 60W, Coatamine 86W, Coatamine D86P, Sanizol C, Sanizol B-50, etc., and Lion's Alucard 210-80E. , 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, etc. ) Dimethylammonium chloride) is preferred.

(A salt-forming compound consisting of an acid dye and a resin having a cationic group in the side chain)
When the organic dye used in the present invention is an acid dye, it is also preferable to use it as a salt-forming compound composed of an acid dye and a resin having a cationic group in the side chain. A resin having a cationic group in the side chain for obtaining the salt-forming compound (V) used in the present invention will be described.

The resin having a cationic group in the side chain for obtaining the salt-forming compound (V) is not particularly limited as long as it has at least one onium base in the side chain, but a suitable onium salt structure may be used. From the viewpoint of availability, ammonium salt, iodonium salt, sulfonium salt, diazonium salt, and phosphonium salt are preferable, and considering storage stability (thermal stability), ammonium salt, iodonium salt, and sulfonium are preferable. It is more preferably salt. More preferably, it is an ammonium salt.

When a blue coloring composition for a color filter containing a salt-forming compound (V) is prepared and the characteristics as a color filter are exhibited, a resin of the same type as the binder resin constituting the blue coloring composition for a color filter is used. Is desirable. In the present invention, an acrylic resin is preferably used as the binder resin in the coloring composition for a color filter. Therefore, the acrylic resin is used as the resin having a cationic group in the side chain for obtaining the salt-forming compound (V). It is desirable to have.

Further, as the resin having a cationic group in the side chain of the present invention, a vinyl-based resin containing a structural unit represented by the following general formula (40) is used.

General formula (40)

[In the general formula (40), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂ to R ₄ independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, respectively, of R ₂ to R ₄ . Two of them may be combined with each other to form a ring. Q represents an alkylene group, an arylene group, -CONH-R _5- , -COO-R _5- , and R ₅ represents an alkylene group. Y ^- represents an inorganic or organic anion. ]

In the general formula (40), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group in R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group and a cyclohexyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, a hydrogen atom or a methyl group is most preferable as _R1 .

In the general formula (40), R ₂ to R ₄ independently include a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted. Can be mentioned.

Here, examples of the alkyl group in R ₂ to R ₄ include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n. -Tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3 -Tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and crosslinked cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As the alkyl group, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.

Examples of the alkenyl group in R ₂ to R ₄ include a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1). -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.) can be mentioned. As the alkenyl group, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 8 carbon atoms is more preferable.

Examples of the aryl group in R ₂ to R ₄ include a monocyclic aryl group (phenyl, etc.), a fused polycyclic aryl group (naphthyl, anthrasenyl, phenanthrenyl, anthraquinolyl, fluorenyl, naphthoquinolyl, etc.) and an aromatic heterocyclic hydrocarbon. Groups (thienyl (thiophene-derived group), frills (furan-derived group), pyranyl (pyran-derived group), pyridyl (pyridine-derived group), 9-oxoxanthenyl (xanthone-derived group) Induced groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like).

When the alkyl group, alkenyl group and aryl group represented by R ₂ to R ₄ have a substituent, the substituent may be, for example, a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group or an acyl group. Examples thereof include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group and the like. As the substituent, a halogen atom, a hydroxyl group, an alkoxyl group and a phenyl group are particularly preferable.

As R ₂ to R ₄ , alkyl groups which may be substituted from the viewpoint of stability are preferable.
Unsubstituted alkyl groups are more preferred.

Further, two of R ₂ to R ₄ may be bonded to each other to form a ring.

In the general formula (40), the component of Q that connects the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, -CONH-R _5- , -COO-R _5- , and R ₅ represents an alkylene group. Of these, -CONH-R _5- and -COO-R _5- are preferable for the reasons of polymerizable property and availability. Further, it is more preferable that R ₅ is a methylene group, an ethylene group, a propylene group, or a butylene group, and it is particularly preferable that it is an ethylene group.

The component of Y ⁻ in the general formula (40) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be adopted without limitation, and specifically, hydroxide ion; halogen ion such as chloride ion, bromide ion and iodide ion; carboxylic acid ion such as formate ion and acetate ion; Like carbonate ion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, permanganate ion, and even hexacyanoferrate (III) acid ion. Examples thereof include complex ions. From the viewpoint of synthetic aptitude and stability, halogen ions and carboxylic acid ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion may be covalently bonded to the resin to form an intramolecular salt.

The colorant (A) in the present invention preferably contains a red pigment, and two or more kinds of red pigments may be used in combination.

<Resin (B)>
The photosensitive coloring composition for a color filter of the present invention contains a resin (B) containing a resin (B1) obtained by reacting a copolymer of the following (a) and (b) with (c) and then (d). contains. By containing the resin (B1), the occurrence of surface abnormalities can be suppressed even if the monomer (C1) described later is contained in the monomer in a high proportion. In the present invention, these can be used alone or in combination of two or more.
(A): Cyclic ether skeleton having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond (b): A single unsaturated bond different from (a) and having an unsaturated bond copolymerizable with (a). Quantum (c): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (d): Polybasic acid anhydrides

The resin (B1) of the present invention has a cyclic ether skeleton having 2 to 4 carbon atoms and a monomer (a) having an ethylenically unsaturated bond, and an unsaturated bond copolymerizable with (a). At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides in a copolymer with a monomer (b) different from a) (c).
Next, since it has a complicated structure obtained by reacting the polybasic acid anhydride (d) and cannot be represented by a general formula (structure) or is approximately impractical, it is described by a production method. do.

<Resin (B1) in which (c) and then (d) are reacted with the copolymer of (a) and (b)>
[(A): Cyclic ether skeleton having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond]
Examples of (a) include a monomer having an oxylanyl group and an ethylenically unsaturated bond (aX), a monomer having an oxetanyl group and an ethylenically unsaturated bond (aY), a tetrahydrofuryl group and the like. Examples thereof include a monomer (aZ) having an ethylenically unsaturated bond.

(Monomer having an oxylanyl group and an ethylenically unsaturated bond (aX))
Examples of (aX) include a monomer (a-1) having an epoxidized chain olefin and an ethylenically unsaturated bond, and an epoxidized cycloalkene structure and an ethylenically unsaturated bond. The monomer (a-2) having the above can be mentioned.
As (aX), a monomer having an oxylanyl group and a (meth) acryloyloxy group is preferable, and (a-2) having a (meth) acryloyloxy group is more preferable.

Specific examples of (a-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinyl. Benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) Styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glysidyloxymethyl) Styrene, 2,3,5-Tris (Glysidyloxymethyl) Styrene, 2,3,6-Tris (Glysidyloxymethyl) Styrene, 3,4,5-Tris (Glysidyloxymethyl) Styrene, 2, Examples thereof include 4,6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

Examples of (a-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, seroxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), and 3,4-epoxycyclohexylmethyl acrylate (for example, cyclohexyl). Mar A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethylmethyl methacrylate (for example, cyclomer M100; manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (I), the compound represented by the formula (II). ), And the like.

[In formulas (I) and (II), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. It may have been. X ¹ and X ² independently represent a single bond, -R 3-, * -R ³ -O-, * -R ³ -S-, * -R ^{3 -} NH-. R ³ represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. The alkyl groups substituted with hydroxy groups include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy-1. -Methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be mentioned.

Examples of R ¹ and R ² include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.

The X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a * -CH ₂ -O- (* represents a bond with O) group, and a * -CH ₂ CH ₂ -O- group. More preferably, a single bond, * -CH ₂ CH ₂ -O- group may be mentioned.

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15). Preferably, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I-15). Examples thereof include compounds represented by any of the above. More preferably, a compound represented by any one of the formula (I-1), the formula (I-7), the formula (I-9) and the formula (I-15) can be mentioned.

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). Preferably, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15). Examples thereof include compounds represented by any of the above. More preferably, a compound represented by any one of the formula (II-1), the formula (II-7), the formula (II-9) and the formula (II-15) can be mentioned.

The compound represented by the formula (I) and the compound represented by the formula (II) can be used independently. Also, they can be mixed in any ratio. When mixed, the mixing ratio is a molar ratio, preferably the formula (I): formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, and particularly preferably 20:80. ~ 80:20.

(Monomer having an oxetanyl group and an ethylenically unsaturated bond (aY))
As (aY), a monomer having an oxetanyl group and a (meth) acryloyloxy group is preferable. Examples of (a-Y) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and 3-methyl-3- (meth) acryloyloxyethyl. Oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane and the like can be mentioned.

(Monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (aZ))
As (aZ), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (aZ) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

[(B): Monomer different from (a) having an unsaturated bond copolymerizable with (a)]
Examples of (b) include (meth) acrylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Alkyl esters;
Cyclic (meth) acrylic acid cyclic alkyl esters such as cyclohexyl (meth) acrylates, 2-methylcyclohexyl (meth) acrylates, dicyclopentanyl (meth) acrylates, dicyclopentanyloxyethyl (meth) acrylates, and isobornyl (meth) acrylates. Kind;

Aryl (meth) acrylates such as phenyl (meth) acrylates and benzyl (meth) acrylates or aralkyl esters; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid; 2-hydroxyethyl (meth) acrylates, Hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyl) Oxycarbonyl) Bicyclo unsaturated compounds such as bicyclo [2.2.1] hept-2-ene;

N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, as (b), the compound (b1) having an aromatic ring group represented by the general formula (1) or the general formula (2), or the aliphatic ring group represented by the chemical formula (3) or the chemical formula (4) is used. When at least one of the compound (b2) is contained, the chemical resistance is good and the coating film has high hardness.

General formula (1)

［一般式（１）及び（２）中、Ｒ_１は、水素原子又はベンゼン環を有していてもよい炭素数１～２０のアルキル基である。］ General formula (2)

[In the general formulas (1) and (2), R ₁ is an alkyl group having 1 to 20 carbon atoms which may have a hydrogen atom or a benzene ring. ]

Chemical formula (3)

Chemical formula (4)

((B1) A compound having an aromatic ring group represented by the general formula (1) or the general formula (2))
Specific examples of the monomer (b1) having the structures of the general formulas (1) and (2) include styrene, α-methylstyrene, divinylbenzene, inden, acetylnaphthene, benzyl acrylate, benzyl methacrylate, and bisphenol A di. Examples thereof include monomers / oligomers such as glycidyl ether di (meth) acrylate and (meth) acrylic acid ester of methylolated melamine, and ethylenically unsaturated monomers represented by the general formula (5).

［一般式（５）中、Ｒ_６は、水素原子又はメチル基であり、Ｒ_７は、炭素数２又は３のアルキレン基であり、Ｒ_８は、ベンゼン環を有していてもよい炭素数１～２０のアルキル基であり、ｎは、１～１５の整数である。］ General formula (5)

[In the general formula (5), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is an alkylene group having a benzene ring. It is an alkyl group of 1 to 20, and n is an integer of 1 to 15. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (5) include
New Frontier CEA manufactured by Daiichi Kogyo Seiyaku Co., Ltd. [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n = 1 or 2,], NP-2 [n-nonylphenoxypolyethylene] Glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene Group, R ₈ : n-nonyl group, n = 16-17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or Ebecryl110 [ethoxylated phenyl acrylate (EO 2 mol), manufactured by Daicel. R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 2],
Aronix M-101A manufactured by Toa Synthetic Co., Ltd. [Pharmon EO modified (n≈2) acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n≈2], M-102 [Pharmon EO modified (phenol EO modified (n≈2)) _n≈4 ) acrylate, R6: hydrogen atom, _R7 : ethylene group, R8: hydrogen atom, _n≈4 ], M-110 [paracumylphenol EO modified ( _n≈1 ) acrylate, R6: hydrogen atom , R ₇ : ethylene group, R ₈ : paracumyl, n≈1], M-111 [n-nonylphenol EO modified (n≈1) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n- Nonyl group, n≈1], M-113 [n-nonylphenol EO modified ( _n≈4 ) acrylate, R6: hydrogen atom, _R7 : ethylene group, R8: n-nonyl group, _n≈4 ], or M-117 [n-nonylphenol PO modified ( _n≈2.5 ) acrylate, R6: hydrogen atom, _R7 : propylene group, R8: n-nonyl group, _n≈2.5 ],
Kyoei Co., Ltd. Light acrylate PO-A [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], P-200A [phenoxy polyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], NP-4EA [nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4 ], Or NP-8EA [[nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ₆ ]. : Methyl group, R ₇ : Propropylene group, R ₈ : Hydrogen atom, n = 1],
Blemmer ANE-300 manufactured by Nichiyu Co., Ltd. [Nonylphenoxypolyethylene glycol acrylate, R ₆ : Hydrogen atom, _R7 : Ethylene group, R8: _-Nonyl group, n≈5], ANP-300 [Nonylphenoxypolypolyglycol acrylate, R ₆ : Hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, n≈5], 43ANEP-500 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group And propylene group, R ₈ : -nonyl group, n≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n -Nonyl group, n≈9 + 3], 75ANEP- ₆₀₀ [Nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R6: hydrogen atom, _R7 : ethylene group and propylene group, R8: n-nonyl group, _n≈5 + 2 ], AAE-50 [Phenoxypolyethylene glycol acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 1], AAE-300 [Phenoxy polyethylene glycol acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n≈5.5], PAE-50 [Phenoxypolyethylene glycol methacrylate, R ₆ : Methyl group, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 1], PAE-100 [Phenoxypolyethylene glycol methacrylate, R ₆ : Methyl group, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 2], or 43PAPE-600B [Phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R ₆ : Methyl group, R ₇ : ethylene group and propylene group, R ₈ : hydrogen atom, n≈6 + 6],
NK ESTER AMP-10G manufactured by Shin-Nakamura Chemical Co., Ltd. [Phenoxyethylene glycol acrylate ( _EO1 mol), R6: Hydrogen atom, _R7 : Ethylene group, R8: Hydrogen atom, n = ₁ ], AMP-20G [Phenoxyethylene glycol acrylate] (EO 2 mol), R 6: Hydrogen atom, R ₇ : Hydrogen atom, R ₈ : Hydrogen atom, n≈2], AMP-60G [Phenoxyethylene glycol acrylate (EO _{6 mol), R 6 :} Hydrogen atom, R ₇ : Ethylene group , R ₈ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO1 mol), R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Viscoat # 192 manufactured by Osaka Organic Chemical Co., Ltd. [Phenoxyethyl acrylate, R ₆ : Hydrogen atom, R ₇ : Ethylene group, R ₈ : Hydrogen atom, n = 1], or
SR-339A manufactured by Nippon Kayaku Yakuhin SR-339A [2-phenoxyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or SR-504 (ethoxylated nonylphenol acrylate, R ₆ ). : Hydrogen atom, R ₇ : Ethylene group, R ₈ : n-nonyl group] and the like, but the present invention is not limited to these, and two or more types can be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (5), the alkyl group of R8 has ₁ to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the number of carbon atoms of the alkyl group of R ₈ is 1 to 10, the alkyl group becomes an obstacle and suppresses the penetration of the ITO etching solution, the Metal etching solution, etc., and the chemical resistance is enhanced. However, when the number of carbon atoms exceeds 10, the alkyl group of the alkyl group It has a high steric hindrance effect and tends to hinder adhesion to the base material. This tendency becomes remarkable as the carbon chain length of the alkyl group of R8 becomes longer, and when the number of carbon atoms exceeds ₂₀ , the adhesion to the substrate becomes extremely low. Examples of the alkyl group having a benzene ring represented by R ₈ include a benzyl group and a 2-phenyl (iso) propyl group. By increasing the number of side chain benzene rings by one, the chemical resistance is further improved and the developability is also improved.

In the ethylenically unsaturated monomer represented by the general formula (5), n is preferably an integer of 1 to 15. When n exceeds 15, the hydrophilicity is increased, the effect of solvation is reduced, the viscosity of the resin (A) is increased, and the viscosity of the photosensitive composition using the resin (A) is also increased, which affects the fluidity. May be given. From the viewpoint of solvation, n is particularly preferably 1 to 4.

The monomers having the structures of the general formulas (1) and (2) include styrene, α-methylstyrene, benzyl acrylate, and benzyl from the viewpoint of copolymerizability with other monomers and chemical resistance. Methacrylate or ethylenically unsaturated monomer represented by the general formula (5) is preferable. This is because the introduction of the benzene ring into the side chain of the resin (A) prevents the penetration of chemicals due to the stacking effect of the side chain benzene rings and improves the chemical resistance.

((B2) Compound having an aliphatic ring group represented by the chemical formula (3) or the chemical formula (4))
As the monomer (b2) having the structure of the chemical formula (3) or (4), specifically, the ethylenically unsaturated monomer represented by the general formula (6) or the ethylenically represented by the general formula (7). Examples include unsaturated monomers.

General formula (6)

［一般式（６）、一般式（７）中、Ｒ_９は、水素原子又はメチル基であり、Ｒ_１０は、炭素数２又は３のアルキレン基であり、ｍは、１～１５の整数である。］ General formula (7):

[In the general formula (6) and the general formula (7), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. be. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (6) include
Hitachi Kasei Funkrill FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0] or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ ] : None, m = 0] and the like, but the present invention is not limited to these, and two or more types can be used in combination.

Examples of the unsaturated ethylene monomer represented by the general formula (7) include, for example.
Hitachi Kasei Funkrill FA-511A [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], FA-512A [dicyclopentenyl oxyethyl acrylate, R ₉ : hydrogen atom, R ₁₀ ] : Ethyl group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R ₉ : Methyl group, R ₁₀ : Ethyl group, m = 1] and the like can be mentioned, but the present invention is not limited to these, and two or more types can be used in combination.

As (b2), dicyclopentanyl (meth) acrylate is particularly preferable from the viewpoint of chemical resistance and hardness.

[(C): At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride]
Specific examples of (c) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Bicyclounsaturated compounds containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as monosuccinic acid mono [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerizability and alkali solubility.

The addition amount of (c) is preferably 10 to 60% by mass, more preferably 30 to 40% by mass, based on the copolymer obtained by copolymerizing (a) and (b) in terms of the charged value. ..

[(D): Polybasic acid anhydride]
Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, use tricarboxylic acid anhydride such as trimellitic acid anhydride or tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride to obtain the remaining anhydride. It is also possible to hydrolyze the group. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased.

The addition reaction of (d) is carried out by a conventional method. The amount of (d) added is 5 to 100%, preferably 30 to 100%, of the hydroxyl group generated at the time of introducing the photosensitive group. Further, the weight average molecular weight of the resin (B1) is preferably 3,000 or more and 30,000 or less, and more preferably 4,000 or more and 15,000 or less. A strong crosslinked structure can be obtained when the molecular weight is 3,000 or more, and the developability is excellent when the molecular weight is 30,000 or less. Above all, when the weight average molecular weight is 4,000 or more and 15,000 or less, it is possible to achieve both good chemical resistance and high resolution.
Here, the weight average molecular weight is as follows: In the gel permeation chromatography "HLC-8120GPC" manufactured by Tosoh Corporation, four separation columns are connected in series, and the filler is "TSK-GEL SUPER H5000" manufactured by Tosoh Corporation in order. It is a polystyrene-equivalent molecular weight measured by using "H4000", "H3000", and "H2000" and using tetrahydrofuran as a mobile phase.

<Other resins>
The resin (B) of the present invention may contain other resins in addition to the specific resin (B1) as long as the effects are not impaired.
As the other resin, a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm is used. Other resins include thermoplastic resins, thermosetting resins, active energy ray-curable resins having ethylenically unsaturated double bonds, etc. when classified according to their main curing methods, and active energy ray-curable resins are thermal. It may be a plastic resin or one having a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. Further, a thermoplastic resin having no active energy ray curability may be contained, and it is also preferable that the thermoplastic resin is alkaline-soluble. These can be used alone or in combination of two or more. In particular, it is desirable to use a photosensitive resin with alkaline availability and a non-photosensitive resin with alkaline availability in combination.

[Thermoplastic resin]
Examples of the thermoplastic resin that can be used as other resins include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin. And so on.
The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having an acidic group such as a carboxyl group and a sulfone group. Specifically, the resin is an acrylic resin having an acidic group, α-olefin / (anhydrous) maleic acid copolymer, styrene / styrene sulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer, or isobutylene /. (Anhydrous) maleic acid copolymer and the like can be mentioned. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an alkali-soluble resin having an acidic group and / or a hydroxyl group, has developability, heat resistance, and transparency. Since it is expensive, it is preferably used.

[Alkali-soluble resin]
The photosensitive resin composition of the present invention preferably contains an alkali-soluble resin from the viewpoint of developability, heat resistance and transparency. It is intended to impart development solubility in the alkaline development step at the time of producing a color filter, and has an acid group and / or a hydroxyl group. Further, in order to further improve the photosensitivity, it is more preferable to use a resin having an ethylenically unsaturated double bond.

[Alkali-soluble resin with ethylenically unsaturated double bond]
The alkali-soluble resin contained in the photosensitive resin composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin having an ethylenically unsaturated double bond introduced by the method (i) shown below, the resin is crosslinked by three-dimensional crosslinking when exposed to active energy rays to form a coating film. Increases density and improves chemical resistance.

[Method (i): Resin (B2)]
As the method (i), an ethylenically unsaturated monomer having a hydroxyl group is used, and by copolymerizing with another unsaturated monobasic acid monomer having a carboxyl group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the ethylenically unsaturated monomer having an isocyanate group.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or hydroxyalkyl methacrylates such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate can be mentioned, and these may be used alone or in combination of two or more. May be used in combination. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylate to which poly 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 or more and 6 or less hydroxyl groups. Therefore, glycerol mono (meth) acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate. However, the present invention is not limited to these, and two or more types can be used in combination.

Examples of the monomers constituting the alkali-soluble resin include the following. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) (Meta) acrylates such as acrylates, phenoxyethyl (meth) acrylates, phenoxydiethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates, or ethoxypolyethylene glycol (meth) acrylates,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrene, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, vinyl acetate, fatty acid vinyls such as vinyl propionate. And so on.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimideacridin, compounds represented by the following general formula (8), specifically EO-modified cresol acrylate. , N-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenylacrylate, ethyleneoxide (EO) modified (meth) acrylate of phenol, EO or propyleneoxide (PO) modified (meth) acrylate of paracumylphenol, nonylphenol Examples thereof include EO-modified (meth) acrylate and PO-modified (meth) acrylate of nonylphenol.

General formula (8)

(In the general formula (8), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon which may have a benzene ring. It is an alkyl group of the number 1 to 20, and n is an integer of 1 to 15.)

Further, a carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Further, a hydroxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane. Examples thereof include hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added.

Further, a phosphoric acid ester group-containing ethylenically unsaturated monomer can also be used. The phosphoric acid ester group-containing ethylenically unsaturated monomer can be obtained, for example, by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Can be mentioned.

<Alkali-soluble resin (B3) having no ethylenically unsaturated double bond>
The photosensitive resin composition of the present invention can contain an alkali-soluble resin (B3) having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. Ethylene is synthesized by using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers, and not imparting an ethylenically unsaturated bond to the side chain. An alkali-soluble resin having no sex-unsaturated double bond can be obtained.

The alkali-soluble resin in the present invention preferably has a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 3,000 or less, preferably 4,000, in order to impart alkali development solubility. More preferably 20,000 or less. Further, the value of Mw / Mn is preferably 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg / g) in order to impart alkali development solubility, preferably in the range of 70 or more and 180 or less, and more preferably 90 or more and 170 or less. It is a range. When the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.

<Photopolymerizable monomer (C)>
The photosensitive composition of the present invention contains a photopolymerizable monomer (C) containing 8 or more (meth) acryloyl groups in one molecule and a polyfunctional urethane acrylate (C1) having a triazine skeleton. do. The content of the polyfunctional urethane acrylate (C1) is 40 to 100% by mass with respect to the total amount of the photopolymerizable monomer (C). More preferably, it is 45 to 100% by mass. By including the above (C1) in a predetermined range, a photosensitive coloring composition having high linearity and high heat resistance can be obtained. The photopolymerizable monomer includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to form a transparent resin.

(Polyfunctional urethane acrylate (C1) containing 8 or more acryloyl groups and having a triazine skeleton)
The polyfunctional urethane acrylate (C1) may have a urethane bond and eight or more (meth) acrylate groups and a triazine skeleton as the central skeleton, and known ones can be appropriately used.

The polyfunctional urethane acrylate (C1) as described above can be obtained, for example, as a reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and a triazine structure-containing polyfunctional isocyanate. More specifically, a compound having four or more photopolymerizable functional groups and a hydroxyl group having one hydroxyl group in one molecule, and a compound having both two or more isocyanate groups and a triazine structure as a central skeleton. It can be obtained by reacting a compound having three photopolymerizable groups and one hydroxyl group in one molecule, and reacting a compound having both three or more isocyanate groups and a triazine structure as a central skeleton. Can be done.

<< Hydroxy-containing (meth) acrylate >>
Examples of the (meth) acrylate having a hydroxyl group include a compound having one photopolymerizable group and one hydroxyl group in one molecule such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate;
Compounds having two photopolymerizable groups and one hydroxyl group in one molecule, such as trimethylolpropane di (meth) acrylate, glycerol acrylate methacrylate, and glycerol dimethacrylate;
Pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, A compound having three or more photopolymerizable groups and one hydroxyl group in one molecule, such as dipentaerythritol caprolactone-modified penta (meth) acrylate;
A compound having one photopolymerizable group and two hydroxyl groups in one molecule such as glycerin mono (meth) acrylate;
Examples thereof include a compound having two or more photopolymerizable groups and two hydroxyl groups in one molecule such as a reaction product of an epoxy group-containing compound and (meth) acrylic acid.

《Multifunctional isocyanate》
Examples of the polyfunctional isocyanate include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and bifunctional or higher functional isocyanate compounds which are burettes, nurates, and adducts thereof.

Examples of the aromatic diisocyanate include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-. Tolylene diisocyanate, 4,4'-toluidin diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4', 4 "-Triphenylmethane triisocyanate, ω, ω'-diisocyanate-1,3-dimethylbenzene (also known as XDI, m-xylylene diisocyanate), ω, ω'-diisocyanate-1,4-dimethylbenzene (also known as p) -Xylylene diisocyanate), ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.

Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

Examples of the alicyclic diisocyanate include 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate (also known as IPDI, isophorone diisocyanate), 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1, Examples thereof include 4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane and the like.

Examples of the burette body include a burette body of hexamethylene diisocyanate (product name "Sumijour N-75", manufactured by Sumika Bayer Urethane Co., Ltd .; product name "Duranate 24A-90CX", manufactured by Asahi Kasei Chemicals Co., Ltd.).

Examples of the nurate form include a hexamethylene diisocyanate nurate form (product name "Sumijour N-3300", manufactured by Sumika Bayer Urethane Co., Ltd.) and an isophorone diisocyanate nurate form (product name "Death Module Z-4370", Sumika). Bayer Urethane Co., Ltd.), tolylene diisocyanate nurate (product name "Coronate 2030", manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like can be mentioned.

Examples of the adduct body include bifunctional or higher functional isocyanate compounds obtained by reacting the above aromatic isocyanates, aliphatic isocyanates, and / or alicyclic isocyanates with polyfunctional alcohols, and examples thereof include trimethylolpropane. Hexamethylene diisocyanate adduct (product name "Takenate C160N", manufactured by Mitsui Kagaku Co., Ltd.), Trilylene diisocyanate adduct body of trimethylolpropane (product name "Coronate L", manufactured by Nippon Polyurethane Co., Ltd .; Product name "Takenate C102", Mitsui (Manufactured by Kagaku Co., Ltd.), Xylylene diisocyanate adduct of trimethylolpropane (product name "Takenate C110N", manufactured by Mitsui Kagaku Co., Ltd.), Isophorone diisocyanate adduct of trimethylolpropane (product name "Takenate C140N", manufactured by Mitsui Kagaku Co., Ltd.), etc. Can be mentioned.

《Multifunctional alcohol》
The polyfunctional alcohol has a reaction with the (meth) acrylate having an isocyanate group for obtaining the polyfunctional urethane acrylate (C1), and the aromatic isocyanate, the aliphatic isocyanate for obtaining the adduct, and the polyfunctional isocyanate. / Or can be used in a reaction with an alicyclic isocyanate.
Examples of the polyfunctional alcohol include ethylene glycol, propylene glycol diethylene glycol, butylene glycol, 1,6-hexaneglycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptan, and 2-methyl-1. , 8-octanediol, 3,3'-dimethylol heptane, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, 1,5 -Pentandiol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedi Lipid or alicyclic diols such as methanol, tricyclodecanedimethanol, cyclopentadiene dimethanol, dimerdiol;
1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'-methylenediphenol, 4, 4'-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropyridenephenol, or bisphenols such as bisphenol A and bisphenol F Aromatic diols such as bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to
1,1,1-trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, 1,1,1-trimethylolheptan, 1,1,1-Trimethylol Octane, 1,1,1-Trimethylol Nonan, 1,1,1-Trimethylol Decan, 1,1,1-Trimethylol Undecane, 1,1,1-Trimethylol Dodecane, 1,1,1-trimethylolpropane, 1,1,1-trimethyloltetradecane, 1,1,1-trimethylolpentadecane, 1,1,1-trimethylolhexadecane, 1,1,1-trimethylolhepta Decane, 1,1,1-trimethylol octadecane, 1,1,1-trimethylol nanodecane, 1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1, , 1,1-trimethylol-tert-nonan, 1,1,1-trimethylol-tert-tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl -Hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1, 1,1-Trimethylol branched alcans such as trimethylolisoheptadecane;
Trimethylol Butene, Trimethylol Hepten, Trimethylol Penten, Trimethylol Hexen, Trimethylol Hepten, Trimethylol Octen, Trimethylol Desen, Trimethylol Dodecen, Trimethylol Tridecene, Trimethylol Pentadecene, Trimethylol Hexadecene, Tri Trifunctional polyols such as metrolheptadecene, trimethyloloptadecene, 1,2,6-butanetriol, 1,2,4-butanetriol, glycerin;
Four-functional or higher-functional polyols such as pentaerythritol, dipentaerythritol, sorbitol, and xylitol;
Examples thereof include high molecular weight polyols such as polyester polyols, polycarbonate polyols, polyether polyols, and polyurethane polyols. These polyfunctional alcohols may be used alone or in combination of two or more.

<< Isocyanate group-containing (meth) acrylate >>
Examples of the (meth) acrylate having an isocyanate group include 2-methacryloyloxyethyl isocyanate (product name "Karenzu MOI", manufactured by Showa Denko Co., Ltd.) and 2-acryloyloxyethyl isocyanate (product name "Karenzu AOI", manufactured by Showa Denko Co., Ltd.). A compound having one photopolymerizable group and one isocyanate group in one molecule such as;
1,1- (Bis-acryloyloxymethyl) ethyl isocyanate (product name "Karenzu B"
Examples thereof include compounds having two or more photopolymerizable groups and one isocyanate group in one molecule such as "EI" (manufactured by Showa Denko KK).

<< Compounds with mercapto and carboxyl groups >>
Examples of the compound having a mercapto group and a carboxyl group include thioglycolic acid, 3-mercaptopropionic acid, thioapple acid and the like.

《Hydroxy acid》
Hydroxy acids include glycolic acid, lactic acid, tarthronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, apple acid, citric acid, isocitrate, citramalic acid, leucic acid, ricinolic acid, lysine lysic acid, cerebronic acid, Hydroxy acids with one hydroxyl group such as salicylic acid, cleosortic acid, vanillic acid, syring acid, mandelic acid, benzylic acid, atrolactic acid, melirot acid, kumalic acid, ferulic acid, cinnapic acid;
Examples thereof include hydroxy acids having two or more hydroxyl groups such as tartrate acid, mevalonic acid, pantoic acid, shikimic acid, pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentidic acid, orsellinic acid, coffee acid, and umberic acid.

Hydroxy acids can be obtained by reacting some hydroxyl groups of polyfunctional alcohols with polybasic acid anhydrides. Examples of the polyfunctional alcohol include those shown above.
The polybasic acid anhydride is not particularly limited as long as it is a compound containing one or more acid anhydride groups in the molecule. For example, succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic acid anhydride, dodecyl succinic acid anhydride, butyl male acid anhydride, pentyl male acid anhydride, hexyl. Maleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic acid anhydride, butylglutamic acid anhydride, hexylglutamic acid anhydride, heptylglutamic acid anhydride, octylglutamic acid anhydride, decylglutamic acid anhydride, dodecylglutamic acid. Anhydrous dibasic acid anhydride such as anhydrate;
Methyltetrahydrohydroan phthalic acid, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl anhydride nagic acid, anhydrous nagic acid, hydride methylanhydride nagic acid, still-end styrene tetrahydroanhydride phthalic acid, trialkyltetrahydro Alicyclic dibasic acid anhydride such as phthalic anhydride;
An alicyclic polybasic acid anhydride of tribasic acid or more such as hydrogenated trimellitic acid anhydride;
Aromatic dibasic acid anhydrides such as phthalic anhydride and tetrabromophthalic anhydride;
Examples thereof include aromatic polybasic acid anhydrides having a trimellitic acid or more such as trimellitic anhydride.

The photopolymerizable monomer that can be used in the coloring composition of the present invention includes, in addition to the above-mentioned polyfunctional urethane acrylate (C1), when the polyfunctional isocyanate is reacted with the (meth) acrylate having a hydroxyl group. Meta) A component having a double bond group, which was not obtained as a polyfunctional urethane acrylate having an acryloyl group, may be contained as another monomer.

(Other photopolymerizable monomers)
In the present invention, the following photopolymerizable monomers or oligomers can also be used in combination with the acid group-containing polyfunctional urethane acrylate (C1). For example, methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth). ) Acrylate, Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Triethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Trimethylol propantri (meth) acrylate, Pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa. Various acrylic acid esters such as (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, acid group-free urethane acrylate, and methacrylic acid ester. , (Meta) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. ..

The content of the photopolymerizable monomer (C) is preferably 7 to 50% by mass, more preferably 10 to 40% by mass, based on the solid content weight of the coloring composition. Within this range, both light sensitivity and curing shrinkage can be achieved, which is preferable from the viewpoint of adhesion.

<Photopolymerization initiator (D)>
The photosensitive composition of the present invention contains a photopolymerization initiator (D). The photopolymerization initiator is a compound that generates an active species capable of initiating the polymerization of the photopolymerizable monomer by exposure to ultraviolet rays, visible rays, far ultraviolet rays, electron beams, X-rays and the like.

Examples of such a photopolymerization initiator (D) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl. Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4) -Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, etc. Acetphenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicization. Benzophenone compounds such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-Piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6 -Triazine compounds such as triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2) , 4,6-trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; Borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanosen-based compounds are used.
These photopolymerization initiators (D) can be used alone or in admixture of two or more at any ratio, if necessary.

The content of the photopolymerization initiator (D) is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the colorant (A), and is 10 to 150 parts by mass from the viewpoint of photocurability and developability. Is more preferable.

It is preferable to include an oxime ester as the reaction site of the photopolymerization initiator (D) in order to obtain higher linearity.

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, aclysine derivatives, azine derivatives, thiadine derivatives, oxadin derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizer described in "Special Functional Materials" (1986, CMC) can be mentioned, but is not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more kinds of sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount is preferably 3 to 60% by mass based on the total weight of the photopolymerization initiator contained in the coloring composition (100% by mass), and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50% by mass.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd., BYK-333 manufactured by Big Chemie Co., Ltd., and the like. Specific examples of the dimethylsiloxane having a polyester structure include BYK-310 and BYK-370 manufactured by Big Chemie. Didimethylsiloxane having a polyether structure and dimethylsiloxane having a polyester structure can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on the total weight of the coloring composition (100% by mass).

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, it is particularly preferable. It is useful to have a characteristic that its surface tension lowering ability is low, and that it has good wettability to a glass plate despite its low surface tension lowering ability, and an addition amount that does not cause defects in the coating film due to foaming. A substance capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The binding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are repeatedly bonded alternately. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Esther and the like can be mentioned.

Examples of the chaotic surfactant added as an auxiliary to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphoric acid ester, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolin, and fluorocarbon and silicone-based surfactants.

<Antioxidant (E)>
The photosensitive composition of the present invention may contain an antioxidant (E).
The antioxidant (E) in the present invention may be a compound having an ultraviolet absorbing function, a radical catching function, or a peroxide decomposition function, and specifically, the antioxidant is a hindered phenolic agent or a hindered amine. Examples thereof include based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the preferred ones are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants. Agents are mentioned.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Phenol) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
Specific examples include Adecastab AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320 manufactured by ADEKA Co., Ltd., KEMINOX101 179, 76, 9425 manufactured by Chemipro Co., Ltd., IRGANOX1010, 1035 manufactured by BASF Co., Ltd. Examples thereof include 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, and Sianox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd.

Examples of the hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like can be mentioned. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.
Specific examples include Adecastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, manufactured by ADEKA Co., Ltd. LA-402F, LA-502XP, KAMISTAB29, 62, 77, 29, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100 manufactured by BASF Co., Ltd., Siasorb UV-3346, UV manufactured by Sun Chemical Co., Ltd. -3259, UV-3853 and the like can be mentioned.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phenylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, 4,4'isopropyridendiphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) Pentaerythritol diphosphite, Phenylbisphenol A Pentaerythritol diphosphite, Tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, Hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.
Specific examples include ADEKA Corporation ADEKA STAB PEP-36, PEP-8, HP-10, ADEKA STAB 2112, 1178, 1500, C, 3013, TPP, BASF Corporation IRGAFOS168, Clariant Chemicals Corporation HostanoxP-EPQ, etc. Can be mentioned.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.
Specific examples include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

As the benzotriazole-based antioxidant, an oligomer-type compound and a polymer-type compound having a benzotriazole structure can be used.
Specific examples include ADEKA Corporation LA-29, LA-31RG, LA-32, LA-36, -412S, ChemiPro Kasei Co., Ltd. KEMISORB71, 73, 74, 79, 279, and BASF Co., Ltd. TINUVIN PS. , 99-2, 384-2, 900, 928, 1130 and the like.

Benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4. -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 Examples thereof include -methoxy-5 sulfobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.
Specific examples include ADEKA TAB 1413 manufactured by ADEKA Corporation, KEMISORB10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., UV-329 and the like.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Specific examples thereof include ADEKA Corporation LA-46 and F70, KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405, 460, 477, 479 manufactured by BASF Co., Ltd., and Siasorb UV-1164 manufactured by Sun Chemical Co., Ltd. ..

Examples of the salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

These antioxidants can be used alone or in admixture of two or more at any ratio as required. Among the antioxidants, the contact holes are less likely to be closed by increasing the amount of the initiator, and radicals. Most preferred are hindered phenolic antioxidants that can better capture.

The antioxidant (E) is preferably 0.1 to 5.0% by mass with respect to the total solid content of the photosensitive coloring composition. By being in this range, the pattern linearity is excellent and the pattern is not chipped. More preferably, it is 1.0 to 3.0% by mass.

<Thermosetting agent>
The photosensitive coloring composition of the present invention may contain a thermosetting agent containing an epoxy group or an oxetane group, if necessary, in order to assist the curing of the thermosetting resin, and an epoxy compound is particularly preferable. The epoxy compound in the present invention refers to a compound having an epoxy group. The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Further, the epoxy compound is preferably used in an amount of 0.1 to 15.0% by mass based on the solid content weight of the coloring composition for a color filter (100% by mass).

(Epoxy compound)
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) and phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy). Weight of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) with benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. Condensates, phenols and polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols Polycondensates of s and ketones (acetones, methyl ethyl ketones, methylisobutylketones, acetophenones, benzophenones, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol , Biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) Examples thereof include polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy compounds obtained by glycidylizing alcohols, alicyclic epoxy compounds, glycidylamine-based epoxy compounds, and glycidyl ester-based epoxy compounds. However, the epoxy compound is not limited to these as long as it is a commonly used epoxy compound. These may be used alone or may use two or more kinds.

Examples of commercially available products include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P, Epicoat 1004, Epicoat 1256 (the above are trade names; manufactured by Mitsubishi Chemical Corporation), TECHMORE VG3101L ( Product name: Mitsui Kagaku Co., Ltd., EPPN-501H, 502H (trade name: Nippon Kayaku Co., Ltd.), JER 1032H60, JER 157S65, 157S70 (trade name: Mitsubishi Chemical Co., Ltd.), EPPN- 201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (the above are products) Name: Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (trade name: Daicel Co., Ltd.), Denacol EX-810, EX-830, EX-851, EX-611, EX-512 , EX-421, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation) and the like, but are not limited thereto.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improving agent such as a silane coupling agent can be contained in order to improve the adhesion to the transparent substrate. Further, a polymerization inhibitor may be contained in order to prevent the mask from being exposed to light by diffracted light during exposure.

Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

Examples of the adhesion improver include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3,). 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by mass based on the total amount of the colorant in the coloring composition (100% by mass).

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-propylcatechol. , 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert- Alkyl catechol compounds such as butyl catechol, 3,5-di-tert-butyl catechol, 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, Alkyl resorcinol compounds such as 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2, Alkylhydroquinone compounds such as 5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, phosphines such as trioctylphosphine oxide and triphenylphosphine oxide. Examples thereof include phosphite compounds such as oxide compounds, triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucin. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass with respect to 100 parts by mass by weight of the coloring composition excluding the solvent.

<Solvent>
In the photosensitive coloring composition of the present invention, the colorant (A) is sufficiently dispersed in a dye carrier such as a resin (B) or a photopolymerizable compound (C), and a dry film is formed on a transparent substrate such as a glass substrate. A solvent can be contained to facilitate the formation of filter segments or black matrices by coating to a thickness of 0.2-10 μm. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-Propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene , N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o- Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate , Diisobutylketone, Diethylene glycol diethyl ether, Diethylene glycol dimethyl ether, Diethylene glycol monoisopropyl ether, Diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether, Cyclohexanol, Cyclohexanol acetate, Cyclohexanone, Dipropylene glycol dimethyl ether, Dipropylene glycol Dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monobutyl Ether, Propylene Glycol Monopropyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monomethyl Ether Propionate, benzyl Alcohol, Methyl Isobutyl Ketone, Methyl Cyclohexanol, Acetate Examples thereof include n-amyl, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like, and these are used alone or in combination.

The solvent can be used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass with respect to 100 parts by mass of the colorant (A) in the photosensitive coloring composition.

<Manufacturing method of coloring composition>
The coloring composition of the present invention comprises a kneader, a two-roll mill, a three-roll mill, in which the colorant (A) is placed in a colorant carrier such as the resin (B) and / or a solvent, preferably with a dispersion aid. It can be finely dispersed and produced by using various dispersion means such as a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or separately dispersed in the colorant carrier may be mixed.
If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a resin-type dispersant, a dye derivative, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high lightness and viscosity stability. Become good.

[Resin type dispersant]
The resin-type dispersant has a colorant-affinitive moiety having a property of adsorbing to the additive colorant and a moiety compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed on the colorant carrier. It works to stabilize. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamidophosphate, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oily dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphate ester-based, etc. are used, and these can be used alone or in admixture of two or more. However, it is not necessarily limited to these.

As the dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, such as a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, and a nitrogen-containing heterocycle. A nitrogen atom-containing acrylic block copolymer and a urethane-based polymer dispersant having a functional group containing the above are preferable. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film forming property.

The basic resin-type dispersant having an amino group corresponds to the above-mentioned amino group-containing resin (I).

Further, the resin-type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin-type dispersant having a carboxyl group.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride.
(S2) A weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. A resin-type dispersant that is a coalescence.

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, JP-A-2008-029901, and JP-A-2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that the number of hydroxyl groups at the terminal is plural, the compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example, a polymer having two hydroxyl groups at one end contains a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained therein. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and the carboxylic acid. Produces.

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and the like, for example, a compound having a hydroxyl group. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. can get. Above all, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. The molecular weight and the like may differ slightly depending on various conditions, but if the reaction conditions are the same as those of the raw material, the same can be theoretically obtained.

[Dye derivative]
As the dye derivative used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, compounds having an acidic functional group such as a sulfo group, a carboxy group and a phosphoric acid group, amine salts thereof, compounds having a basic functional group such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group and a phthalimide. Examples thereof include compounds having a neutral functional group such as an alkyl group. Japanese Patent Application Laid-Open No. 63-305173, Japanese Patent Application Laid-Open No. 57-15620, Japanese Patent Application Laid-Open No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Patent Application Laid-Open No. 5-9469, Japanese Patent Application Laid-Open No. 2001-335717, Japanese Patent Application Laid-Open No. Kai 2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094873, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008 -195916, Japanese Patent No. 4585781, Japanese Patent Application Laid-Open No. 2006-291194, Japanese Patent Application Laid-Open No. 2007-226161, Japanese Patent Application Laid-Open No. 2007-314681, Japanese Patent Application Laid-Open No. 2007-314785, Japanese Patent Application Laid-Open No. 2012-226110. , Japanese Patent Application Laid-Open No. 2017-165820, Japanese Patent Application Laid-Open No. 2005-181383, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, a neutral group, and the like. A compound having a functional group of is synonymous with a dye derivative. In addition, these can be used alone or in combination of two or more.

From the viewpoint of improving dispersibility, the content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

[Surfactant]
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalrine sulfonate, and sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When the surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by mass, the dispersion may be affected by the excess dispersant. ..

<Removal of coarse particles>
The colored composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Color filter>
The color filter of the present invention is a color filter comprising at least one filter segment formed by the coloring composition for a color filter of the present invention. The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one filter segment comprises the coloring composition for a color filter of the present invention. It is preferably formed using.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method.

The formation of filter segments by the printing method can be patterned simply by repeating printing and drying of the coloring composition prepared as printing ink, so that it is low cost and excellent in mass productivity as a manufacturing method of color filters. There is. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

The coloring composition of the present invention is applied onto a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, or the like so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a potassium hydroxide developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

If a black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the display panel can be further enhanced. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the brightness can be improved.
An overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

The color filter is bonded to the facing substrate using a sealing agent, the liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. By laminating, a liquid crystal display panel is manufactured.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optical convensend bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

First, a method for measuring the weight average molecular weight (Mw) of the resin and the acid value of the resin, and a method for calculating the number of urethane groups of the photopolymerizable monomer and the number of double bond groups of the photopolymerizable monomer will be described. ..

<Weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) of the resin was converted into polystyrene measured using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, TSK-GELSUPERHZM-N as a column connected in two series, and THF as a solvent. It is a molecular weight.

<Acid value of resin (mgKOH / g)>
The acid value of the resin is a value obtained by converting the measured acid value (mgKOH / g) into a solid content in accordance with the potentiometric titration method of JISK0070.

First, a photopolymerizable monomer, a resin, a colorant, a pigment dispersion, and a method for producing a photosensitive green coloring composition used in Examples and Comparative Examples will be described.

<Manufacturing of photopolymerizable monomer (C)>
(Photopolymerizable monomer (C1-1))
In the present invention, "U-15HA" manufactured by Shin-Nakamura Chemical Co., Ltd. was used as the photopolymerizable monomer (C1-1). "U-15HA" is a polyfunctional urethane acrylate containing 15 acryloyl groups and having a triazine skeleton.

(Photopolymerizable monomer (C1-2))
In a 2 L volume four-necked flask, 112 g of tris (2-hydroxyethyl) isocyanurate, 216 g of hexamethylene diisocyanate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged, and the temperature was 70 ° C. The reaction was carried out at temperature for 8 hours. Further, 673 g of dipentaerythritol pentaacrylate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged and reacted at a temperature of 70 ° C. for 8 hours, and the disappearance of isocyanate absorption was eliminated by IR analysis. After confirmation, a photopolymerizable monomer (C1-2), which is a polyfunctional urethane acrylate containing 15 acryloyl groups and having a triazine skeleton, was obtained. In addition, it was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(Photopolymerizable monomer (C1-3))
In a 2 L four-necked flask, 157 g of tris (2-hydroxyethyl) isocyanurate, 304 g of hexamethylene diisocyanate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged, and the temperature was 70 ° C. The reaction was carried out at temperature for 8 hours. Furthermore, 539 g of pentaerythritol triacrylate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged and reacted at a temperature of 70 ° C. for 8 hours, and the disappearance of isocyanate absorption was confirmed by IR analysis. A photopolymerizable monomer (C1-3), which is a polyfunctional urethane acrylate containing 9 acryloyl groups and having a triazine skeleton, was obtained. In addition, it was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(Photopolymerizable Monomer (C2-1))
In a 2 L four-necked flask, 191 g of tris (2-hydroxyethyl) isocyanurate, 369 g of hexamethylene diisocyanate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged, and the temperature was 70 ° C. The reaction was carried out at temperature for 8 hours. Further, 439 g of glycerol diacrylate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged and reacted at a temperature of 70 ° C. for 8 hours, and the disappearance of isocyanate absorption was confirmed by IR analysis. , A photopolymerizable monomer (C2-1) which is a polyfunctional urethane acrylate having 6 acryloyl groups and a triazine skeleton was obtained. In addition, it was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(Photopolymerizable monomer (C2-2))
In a 2 L four-necked flask, 862 g of dipentaerythritol pentaacrylate, 138 g of hexamethylene diisocyanate, 1.0 g of N, N-dimethylbenzylamine, and 1.0 g of 4-methoxyphenol were charged, and the temperature was 70 ° C. for 8 hours. After the reaction, disappearance of isocyanate absorption was confirmed by IR analysis, and a photopolymerizable monomer (C2-2), which is a polyfunctional urethane acrylate having 10 acryloyl groups and no triazine skeleton, was obtained. In addition, it was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

A list of the photopolymerized monomers (C1-2 to 3, C2-1 to 2) is shown in Table 1.

The abbreviations in Table 1 are shown below.
DPPA: Dipentaerythritol Pentaacrylate PTA: Pentaerythritol Triacrylate GDA: Gglycerol Diacrylate HDI: Hexamethylene diisocyanate THEI: Tris (2-hydroxyethyl) isocyanurate DMBA: N, N-dimethylbenzylamine MQ: 4-methoxyphenol

<Manufacturing of resin (B)>
(Photosensitive acrylic resin solution (B1-1))
Put 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas introduction tube, and stirrer in a separate 4-neck flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, at the same temperature, a mixture of 14 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 57 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage was added from the dropping tube. The mixture was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, and 29 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. for 5 hours. The reaction was carried out to obtain a resin solution having a weight average molecular weight (Mw) of about 10,500. Since the added acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate constituent unit, no carboxyl group is generated in the resin structure.
Further, 46 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleavage of the carboxylic acid anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.
Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% by mass to obtain an acrylic resin solution (B1-1). The weight average molecular weight (Mw) was 11,500 and the acid value was 103 mgKOH / g.

(Photosensitive acrylic resin solution (B1-2))
Put 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas introduction tube, and stirrer in a separate 4-neck flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, at the same temperature, a mixture of 10 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 61 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage was added from the dropping tube. The mixture was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, and 29 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. for 5 hours. The reaction was carried out to obtain a resin solution having a weight average molecular weight (Mw) of about 7,500. Since the added acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate constituent unit, no carboxyl group is generated in the resin structure.
Further, 46 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleavage of the carboxylic acid anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.
Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% by mass to obtain an acrylic resin solution (B1-2). The weight average molecular weight (Mw) was 8,500 and the acid value was 79 mgKOH / g.

(Photosensitive acrylic resin solution (B1-3))
Put 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas introduction tube, and stirrer in a separate 4-neck flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, at the same temperature, a mixture of 10 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 61 parts of glycidyl methacrylate and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage was added from the dropping tube. The mixture was added dropwise over 5.0 hours to carry out a polymerization reaction.
Next, the inside of the flask was replaced with air, and 29 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. for 5 hours. The reaction was carried out to obtain a resin solution having a weight average molecular weight (Mw) of about 30,500. Since the added acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate constituent unit, no carboxyl group is generated in the resin structure.
Further, 46 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleavage of the carboxylic acid anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.
Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% by mass to obtain an acrylic resin solution (B1-3). The weight average molecular weight (Mw) was 31,500, and the acid value was 101 mgKOH / g.

(Photosensitive acrylic resin solution (B2))
Put 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas introduction tube, and stirrer in a separate 4-neck flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. Then, at the same temperature, a mixture of 14 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 57 parts of methacrylic acid and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage was added from the dropping tube. The mixture was added dropwise over 2.5 hours to carry out a polymerization reaction. The reaction was carried out at 120 ° C. for 5 hours to obtain a resin solution having a weight average molecular weight (Mw) of about 10,500.
Further, 46 parts of glycidyl methacrylate and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. The added tetraglycidyl methacrylate reacts with the carboxyl group in the resin to form a C = C double bond site.
Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% by mass to obtain an acrylic resin solution (B2). The weight average molecular weight (Mw) was 12,500 and the acid value was 90 mgKOH / g.

(Non-photosensitive acrylic resin solution (B3))
200 parts of propylene glycol monoethyl ether acetate was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, heated to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. After that, 14 parts of dicyclopentanyl methacrylate ("Funkryl FA-513AS" manufactured by Hitachi Chemical Co., Ltd.), 70 parts of benzyl methacrylate, 16 parts of methacrylic acid, 2,2'-azobisisobutyronitrile 6 from the dropping tube. A mixture of 0.0 parts was added dropwise over 2 hours and reacted for 3 hours to obtain a solution of an acrylic resin having a solid content of 60% by mass, a weight average molecular weight of 6,500 and an acid value of 106 mgKOH / g.
After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. Etheracetate was added to obtain a non-photosensitive acrylic resin solution (B3) which is an alkali-soluble resin.

<Manufacturing of colorant (A)>
(Red refined pigment (PR-1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of red micronized pigment (PR-1) was obtained.

(Red refined pigment (PR-2))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 269, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8 liters of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. , 190 parts of red micronized pigment (PR-2) was obtained.

(Red refined pigment (PR-3))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 C.I. I. A red finer pigment (PR-3) was obtained in the same procedure as the red finer pigment (PR-1) except that it was replaced with Pigment Red 177.

(Yellow miniaturized pigment (PY-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 yellow pigment C.I. I. Pigment Yellow 138 (BASF "Pariotor Yellow L 0962 HD") was used to obtain a yellow finer pigment (PY-1) in the same procedure as the red finer pigment (PR-1).

(Yellow miniaturized pigment (PY-2))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 yellow pigment C.I. I. Pigment Yellow 150 (“E-4GN” manufactured by LANXESS) was used to obtain a yellow finer pigment (PY-2) in the same procedure as the red finer pigment (PR-1).

(Yellow miniaturized pigment (PY-3))
A quinophthalone compound represented by the following formula (9) was synthesized according to the synthesis method described in Example 8 of JP-A-2012-226110 to give a yellow pigment 1. Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was obtained, and the yellow pigment (PY-3) was obtained in the same procedure as the red fine pigment (PR-1) except that the yellow pigment 1 was replaced.

Equation (9)

(Green refined pigment (PG-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was replaced with a halogenated zinc phthalocyanine green pigment (CI Pigment Green 58), but the green finer pigment (PG-1) was prepared in the same procedure as the red finer pigment (PR-1). Obtained.

(Green fine pigment (PG-2))
To a three-necked flask, add 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (10), 500 parts of N-methylpyrrolidone, and 13.9 parts of diphenyl phosphate, and heat to 90 ° C. It was allowed to react for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a green pigment 1 which is a phthalocyanine pigment.
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was obtained in the same procedure as the red finer pigment (PR-1) except that the green pigment 1 was replaced with the green finer pigment (PG-2).

Equation (10)

(Green fine pigment (PG-3))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the above formula (10), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 20 ° C. for 6 hours. Then, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and a sampled residue were added, and the mixture was stirred at 80 ° C. for 1 hour. Then, the mixture was collected by filtration, washed with water, and dried to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring. Next, to a three-necked flask, 500 parts of N-methylpyrrolidone, 50 parts of a pigment in which an average of 10.1 bromine atoms were substituted on the obtained phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added, and 90 parts were added. It was heated to ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a green pigment 2 which is a phthalocyanine pigment.
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 was obtained in the same procedure as the red finer pigment (PR-1) except that the green pigment 2 was replaced with the green finer pigment (PG-3).

(Blue refined pigment (PB-1))
To 1000 parts of 98% sulfuric acid, 90 parts of crude copper phthalocyanine synthesized by a known method and 10 parts of the dispersant represented by the formula (11) were added, stirred at 30 ° C. for 2 hours, and then 5000 parts using an aspirator. It was mixed with water to obtain an aqueous solution in which copper phthalocyanine particles were precipitated. The obtained aqueous solution was stirred for 30 minutes, then filtered, washed with water, dried and pulverized to obtain 95 parts of a blue fine pigment (PB-1).

Equation (11)

(Blue refined pigment (PB-2))
85 parts of crude copper phthalocyanine synthesized by a known method, 15 parts of the dispersant represented by the above formula (11), 1000 parts of sodium chloride, and 280 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader manufactured by Inoue Seisakusho for 8 hours at 70 ° C. Kneaded. After kneading, the mixture was taken out into 20000 parts of an aqueous buffer solution of acetic acid-sodium acetate (pH 4.0) at 45 ° C., kept warm for 1 hour, and then filtered, washed with water, dried and pulverized to obtain 96 parts of a blue fine pigment (PB-2). ..

(Blue refined pigment (PB-3))
95 parts of ε-type copper phthalocyanine pigment "LIONOL BLUE E" manufactured by Toyo Color Co., Ltd., 5 parts of dispersant represented by the formula (11), 1000 parts of sodium chloride, and 280 parts of diethylene glycol are charged in 1 gallon kneader of stainless steel manufactured by Inoue Seisakusho. , 80 ° C. for 10 hours. After kneading, take out to 20000 parts of a buffer aqueous solution of acetic acid-sodium acetate (pH 4.0) at 30 ° C., heat-retain and stir for 1 hour, then filter, wash with water, dry and pulverize to obtain 96 parts of blue fine pigment (PB-3). rice field.

(Salt dye compound (AR-1))
With reference to Production Example 50 of Japanese Patent Application Laid-Open No. 2011-261667, C.I. I. A salt-forming dye compound (AR-1) composed of Acid Red 52 and an acrylic resin having a cationic group (quaternary ammonium base) in the side chain was produced.

(Salt dye compound (AR-2))
With reference to Production Example 29 of Japanese Patent Application No. 2011-261667, C.I. I. A salt-forming dye compound (AR-2) composed of Acid Red 289 and an acrylic resin having a cationic group (quaternary ammonium base) in the side chain was produced.

(Purple miniaturized pigment (PV-1))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (PV23) (Clariant's "Fast Violet RL") 500 parts, sodium chloride 2500 parts, and polyethylene glycol (Tokyo Kasei Co., Ltd.) 250 parts were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho). It was kneaded at 120 ° C. for 12 hours. Next, this mixture was put into about 5 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, and then filtered and washed with water to remove sodium chloride and diethylene glycol. The mixture was dried at 80 ° C. for 24 hours to obtain a purple finely divided pigment (PV-1).

<Manufacturing of pigment dispersant>
(Pigment Dispersant Solution (K-1))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of propylene glycol monomethyl ether acetate were charged as the first stage synthesis, and nitrogen gas was charged. Replaced with. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2'-azobisisobutyronitrile was divided into 20 portions and 30 times. It was added every minute and reacted at 80 ° C. for 12 hours, and it was confirmed by solid content measurement that 95% of the reaction occurred.
Next, as the second stage synthesis, 30 parts of pyromellitic acid anhydride, 190 parts of propylene glycol monomethyl ether acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. It was added and reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. In this way, an acidic resin-type pigment dispersant having a poly (meth) acrylate skeleton having an acid value of 42 mgKOH / g per solid content and a weight average molecular weight of 9,800 and a non-volatile content of 40% by mass and having an aromatic carboxyl group. A solution (K-1) was obtained.

(Pigment Dispersant Solution (K-2))
A propylene glycol monomethyl ether acetate solution adjusted so that the non-volatile content of EFKA4300 (manufactured by BASF: a basic resin-type dispersant (corresponding to an amino group-containing resin) is 40% by mass.

<Manufacturing of pigment dispersion containing colorant (A)>
(Pigment dispersion (A-R1))
After uniformly stirring and mixing 14.0 parts of the red finely divided pigment (PR-1), 15.0 parts of the pigment dispersant solution (K-1), and 71.0 parts of ethylene glycol monomethyl ether acetate (PGMAc). , Using zirconia beads with a diameter of 0.5 mm, disperse with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then filter with a 5 μm filter to obtain a pigment dispersion (A-R1) of PR254. ) Was obtained.

(Pigment Dispersions A-R2-6, AB1-3, A-Y1-3-3, AG1-3, AV3)
The pigment dispersions A-R2 to 6, AB1 to 3, A- Y1 to 3, A-G1 to 3, and A-V3 were obtained.

(Dye solution AV1-2)
For A-V1 and 2, each material was mixed and stirred at the formulation ratios shown in Table 1 and filtered through a 1 μm filter to obtain dye solutions of each color.

The abbreviations in Table 2 are shown below.
PGMAC: Propylene Glycol Monomethyl Ether Acetate

<Manufacturing of photosensitive coloring compositions for color filters>
[Examples 1 to 19 and Comparative Examples 1 to 6]
Each material was mixed and stirred at the formulation ratios shown in Table 3-5, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color. In this specification, Example 9 is a reference example.

<Evaluation of photosensitive coloring composition>
The surface smoothness, linearity, and heat resistance of the obtained photosensitive coloring composition were evaluated by the following methods. The results are shown in Table 3-5.

(Formation of filter segment)
The obtained coloring composition for a color filter has a thickness after drying using a spin coater on a substrate having a silicon nitride film formed on the surface of a 100 mm × 100 mm, 0.7 mm thick TFT liquid crystal display driving substrate. The coating was applied at a rotation speed of 3.0 μm, dried under reduced pressure, and then exposed to ultraviolet rays using an ultrahigh pressure mercury lamp with an integrated light amount of 40 mJ and an illuminance of 30 mW via a photomask. Then, using a 0.2 mass% sodium carbonate aqueous solution as a developer, the uncured portion of the coating film was removed by a shower development method at a developer pressure of 0.1 mPa, and a regular octagonal through hole having a diameter of 30 μm and a line width of 50 μm were removed. A pattern containing thin lines was formed. Then, the evaluation substrate was prepared by post-baking at 230 ° C. for red: 60 minutes, green: 40 minutes, and blue: 20 minutes. The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

(Evaluation of surface smoothness)
The presence or absence of foreign matter or wrinkles on the pattern coating film was visually confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.).
The evaluation was made in the following three stages.
⊚: No foreign matter and wrinkles on the coating film surface ○: Some foreign matter and wrinkles are generated on the coating film surface ×: Foreign matter and wrinkles are remarkably observed on the coating film surface.

(Evaluation of linearity)
The degree of linearity of the pattern coating film was visually confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.).
⊚: There is no abnormality in the fringe part of the pattern coating film.
◯: Some development residue is seen in the fringe portion of the pattern coating film.
Δ: A remarkable development residue or a defect in the coating film can be confirmed in the fringe portion of the pattern coating film.
X: Remarkable development residue and defect of the coating film can be confirmed in the fringe portion of the pattern coating film.

(Heat resistance evaluation)
The obtained substrate was heated in an oven at 240 ° C. for 1 hour, and the color difference 2 (L ^* (2), a ^* (2), b ^* (2)) was measured with a C light source. Using the measured color difference value, the color difference change rate ΔEab * was calculated by the following formula.
ΔEab ^* = √ ((L ^* (2)-L ^* (1)) ² + (a ^* (2)-a ^* (1)) ² + (b ^* (2)-b ^* (1)) ² )
⊚: ΔEab ^* is less than 3.0 ○: ΔEab ^* is 3.0 or more and less than 5.0 Δ: ΔEab ^* is 5.0 or more and less than 7.0 ×: ΔEab ^* is 7.0 or more

The abbreviations in Table 3-5 are shown below.
Photopolymerizable monomer (C1-1): "U-15HA" manufactured by Shin-Nakamura Chemical Co., Ltd.
Photopolymerizable monomer (DHPA): Dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)

光重合開始剤（Ｄ－３）：ＢＡＳＦ社製「イルガキュア９０７」 Photopolymerization Initiator (D-1): BASF's "Irgacure OXE01"
Photopolymerization initiator (D-2): Photopolymerization initiator represented by the following chemical formula

Photopolymerization Initiator (D-3): BASF's "Irgacure 907"

Antioxidant (E): 2-pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (BASF's "IRGANOX 1010")
Thermosetting agent (F): Propylene glycol of 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol ("EHPE-3150" manufactured by Daicel Corporation) Monomethyl ether acetate solution (adjusted to 20% solid content)
Basic dispersant: EFKA4300 (manufactured by BASF)
Leveling agent: propylene glycol monomethyl ether acetate solution of BYK-330 ("BYK330" manufactured by Big Chemie) (adjusted to a solid content of 1.0%)
PGMAC: Propylene Glycol Monomethyl Ether Acetate EEP: Ethyl-3-ethoxypropionate

The photosensitive coloring composition for a color filter having a specific resin (B1) and a specific photopolymerizable monomer (C1) and having a predetermined range of the photopolymerizable monomer (C1) according to the present invention. The results were good in all items of surface smoothness, straightness, and heat resistance.

Further, from the above results, it was confirmed that the coloring composition for a color filter of the present invention can provide a color filter having high surface smoothness, high straightness, and high heat resistance.

Claims (3)

Colorant (A), resin (B), photopolymerizable monomer (C) and photopolymerization initiation selected from the group consisting of red pigment, yellow pigment, green pigment, blue pigment, purple pigment and salt dye compound. A photosensitive coloring composition for a color filter containing the agent (D).
The resin (B) has an acid value of 50 mgKOH / g or more and 200 mgKOH / g or less, which is obtained by reacting (c) with the following copolymer of (a) and (b) and then reacting with (d). Contains resin (B1),
(A): Cyclic ether skeleton having 2 to 4 carbon atoms and a monomer having an ethylenically unsaturated bond (b): It has an unsaturated bond that can be copolymerized with (a) and is different from (a). Quantum (c): At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (d): Polybasic acid anhydride Photopolymerizable monomer (C) is contained in one molecule. It contains 8 or more (meth) acryloyl groups and contains a polyfunctional urethane acrylate (C1) having a triazine skeleton.
The content of the polyfunctional urethane acrylate (C1) is 40 to 100% by mass with respect to the total amount of the photopolymerizable monomer (C) .
A photosensitive coloring composition for a color filter, wherein the photopolymerization initiator (D) contains an oxime ester-based photopolymerization initiator . The photosensitive coloring composition for a color filter according to claim 1 , further comprising an antioxidant (E). A color filter comprising a filter segment formed from the photosensitive coloring composition for a color filter according to claim 1 or 2 on a substrate.