JP2022086511A - Coloring composition, photosensitive coloring composition, color filter, and solid state image sensor - Google Patents

Abstract

To provide a coloring composition that has excellent viscosity properties and dispersion stability and generates only a small amount of foreign matter; a photosensitive coloring composition that has excellent alkali developability and patternability even when formed into a thin film and contains the coloring composition; a color filter; and a solid state image sensor.SOLUTION: A coloring composition contains an organic pigment (A), a pigment derivative (B), and a dispersion resin (C), the pigment derivative (B) containing a pigment derivative (B1) represented by general formula (1), the dispersion resin (C) containing at least one of a phosphoric acid-based dispersion resin (C1) and a carboxylic acid-based dispersion resin (C2).SELECTED DRAWING: None

Description

The present invention relates to a coloring composition suitable for producing a color filter used for a liquid crystal display device, a solid-state image pickup device, or the like.

A solid-state image sensor represented by C-MOS (Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. is a primary color of an additive mixture of B (blue), G (green), and R (red) on the light receiving element. It is common to arrange each color filter provided with a filter segment and perform color separation. In recent years, the area per pixel tends to be smaller due to the miniaturization and the increase in the number of pixels of the solid-state image sensor, and there is a strong demand for the color filter used in the solid-state image sensor to be thin.

Further, even if the color filter is thinned, the shape of the spectral wavelength is required to remain the same as before. Then, it is necessary to increase the concentration of the organic pigment contained in the pixels of the color filter. For that purpose, it is necessary to increase the concentration of the organic pigment in the photosensitive coloring composition used for producing the color filter.

However, in order to increase the concentration of the organic pigment in the photosensitive coloring composition, it is necessary to reduce other components, and the stability, developability, pattern forming property, coating film resistance, etc. of the photosensitive coloring composition are improved. Problems arise. Therefore, compatibility with thinning has been an issue.

In particular, C.I., which is widely used as an organic pigment for green pixels. I. Since the phthalocyanine green pigments described in Pigment Green 7,36,58,59, JP-A-2016-57635, and JP-A-2016-153481 have low coloring power, the concentration of the organic pigment contained in the pixels is increased. However, it was difficult to make it thinner.

As an effort to reduce the thickness of green pixels, Patent Document 1 discloses a coloring composition using a halogenated zinc phthalocyanine pigment, a quinophthalone pigment, and an azomethine copper pigment in a constant ratio.

JP-A-2015-083664

However, the coloring composition of Patent Document 1 has low coloring power, insufficient thinning while maintaining a spectral waveform, and insufficient viscosity characteristics, dispersion stability, developability, and pattern forming property. When the coating film is heated, there is a problem that foreign matter is generated.

INDUSTRIAL APPLICABILITY The present invention is a coloring composition and a coloring composition which have excellent viscosity characteristics and dispersion stability, are excellent in alkali developability and pattern forming property even in a thin film, and can form a film in which foreign substances are less likely to be generated by heating. The purpose is to provide.

A coloring composition containing an organic pigment (A), a pigment derivative (B), and a dispersed resin (C), wherein the pigment derivative (B) is a pigment derivative (B1) represented by the general formula (1). Including
The present invention relates to a coloring composition containing one or more of a phosphoric acid-based dispersion resin (C1) and a carboxylic acid-based dispersion resin (C2).

[In the general formula (1), one of R ₁ to R ₄ has a substituent represented by the general formula (2), and the other represents a hydrogen atom.
X represents —O— or —NH—, Y represents a divalent linking group containing an unsubstituted alkylene group, and _R5 to _R6 represent an unsubstituted alkyl group. ]

According to the above invention, a coloring composition having excellent viscosity characteristics and dispersion stability, excellent alkali developability and pattern forming property even in a thin film, and capable of forming a film in which foreign matter is unlikely to be generated by heating. A photosensitive coloring composition, a color filter, and a solid-state imaging device can be provided.

The terms used herein will be described. Unless otherwise specified, "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are referred to as "acryloyl and", respectively, unless otherwise specified. / Or metaacryloyl, "acrylic and / or methacrylic acid," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or metaacrylamide." Further, "CI" means a color index. The monomer is a polymerizable unsaturated group-containing compound. The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group and a (meth) acryloyl group.

<Coloring composition>
The coloring composition of the present invention contains an organic pigment (A), a pigment derivative (B), and a dispersed resin (C).
The pigment derivative (B) contains a pigment derivative (B1) represented by the general formula (1).
The dispersion resin (C) is a coloring composition containing one or more of a phosphoric acid-based dispersion resin (C1) and a carboxylic acid-based dispersion resin (C2).

[In the general formula (1), one of R ₁ to R ₄ has a substituent represented by the general formula (2), and the other represents a hydrogen atom.
X represents —O— or —NH—, Y represents a divalent linking group containing an unsubstituted alkylene group, and _R5 to _R6 represent an unsubstituted alkyl group. ]

In the coloring composition of the present invention, the basic substituent in the pigment derivative (B1) represented by the general formula (1) is compatible with the organic pigment (A), so that the dispersion stability of the finely divided pigment particles is stable. In addition to improving, foreign matter is less likely to occur. Further, the synergistic effect with the dispersed resin (C) improves alkali resistance, while improving developability and adhesion.

[Organic pigment (A)]
In the coloring composition of the present invention, the pigment derivative (B1) represented by the general formula (1) has the above-mentioned effect on the entire organic pigment (A), and is an isoindoline pigment (A1) or a phthalocyanine green pigment (A1). Even better effects can be obtained when used in combination with A2).

(Isoindoline pigment (A1))
The coloring composition preferably contains an isoindoline pigment (A1) as the organic pigment (A).
The isoindoline pigment (A1) is, for example, C.I. I. Pigment Yellow 139,185, Pigment Orange 66,69, Pigment Red 260, Pigment Brown 38 and the like. Among these, the isoindoline pigment C.I. I. Pigment Yellow 139,185 is preferred.

The content of the isoindoline pigment (A1) is preferably 20 to 100% by mass, more preferably 20 to 80% by mass, based on 100% by mass of the organic pigment (A).

(Parthalocyanine green pigment (A2))
The coloring composition preferably contains a phthalocyanine green pigment (A2) as the organic pigment (A).
The phthalocyanine green pigment (A2) is, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, JP-A-2016-57635, JP-A-2016-153481, JP-A-2017-197685, and the like. Among these, C.I. I. The phthalocyanine green pigments described in Pigment Green 36,58,59, JP-A-2016-57635, JP-A-2016-153481, and JP-A-2017-197685 are preferable.

The content of the phthalocyanine green pigment (A2) is preferably 20 to 100% by mass, more preferably 30 to 90% by mass, based on 100% by mass of the organic pigment (A).

The coloring composition may contain a pigment other than the isoindoline pigment (A1) and the phthalocyanine green pigment (A2) as the organic pigment (A). Examples of other pigments include yellow pigments (A3), blue pigments (A4), and dyes.

(Yellow pigment (A3))
The yellow pigment (A3) is, for example, C.I. I. Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35: 1,36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97, 98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,147,150, 151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,1822 187,188,193,194,198,199,213,214,218,219,220,221 and the like can be mentioned. Further, examples thereof include quinophthalone pigments described in JP-A-2012-226110 and Japanese Patent No. 6432077. Among these, C. quinophthalone pigment is a quinophthalone pigment from the viewpoint of spectral characteristics and coloring power. I. Pigment Yellow 138, quinophthalone pigments described in JP-A-2012-226110, and Japanese Patent No. 6432077 are preferable.

(Blue pigment (A4))
The blue pigment (A4) is, for example, C.I. I. Bigment 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, 64, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. .. Among these, from the viewpoint of coloring power and pattern formation property, C.I. I. Bigment blue 15: 3, 15: 4, 15: 6 is preferred.

(dye)
The dye is, for example, C.I. I. Solvent Green 1,4,5,7,34,35, C.I. I. Acid Green 1,3,5,9,16,50,58,63,65,80,104,105,106,109, C.I. I. Direct Green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82, C.I. I. Modant Green 1,3,4,5,10,15,26,29,33,34,35,41,43,53, C.I. I. Acid Yellow 2,3,4,5,6,7,8,9,9:1,10,11,11:1,12,13,14,15,16,17,17:1,18,20, 21,22,23,25,26,27,29,30,31,33,34,36,38,39,40,40: 1,41,42,42:1,43,44,46,48, 51,53,55,56,60,63,65,66,67,68,69,72,76,82,83,84,86,87,90,94,105,115,117,122,127, 131,132,136,141,142,143,144,145,146,149,153,159,166,168,169,172,174,175,178,180,183,187,188,189,190, 191,192,199, C.I. I. Direct Yellow 1,2,4,5,12,13,15,20,24,25,26,32,33,34,35,41,42,44,44: 1,45,46,48,49, 50,51,61,66,67,69,70,71,72,73,74,81,84,86,90,91,92,95,107,110,117,118,119,120,121, 126,127,129,132,133,134, C.I. I. Basic Yellow 1,2,5,11,13,14,15,19,21,24,25,28,29,37,40,45,49,51,57,79,87,90,96,103, 105, 106, C.I. I. Solvent Yellow 2,7,28,29,30,32,33,34,40,42,43,44,45,47,48,56,62,64,68,69,71,72,73,77, 79,81,82,83,85,88,89,90,93,94,98,104,107,114,116,117,124,130,131,133,135,138,141,143,1455 146,147,157,160,162,163,167,172,174,175,176,177,179,181,182,183,184,185,186,187,188,190,191,192,194 195, C.I. I. Disperse Yellow 1,2,3,5,7,8,10,11,13,13,23,27,33,34,42,45,48,51,54,56,59,60,63,64 , 67,70,77,79,82,85,88,93,99,114,118,119,122,123,124,126,163,184,184: 1,202,211,229,231,232 , 233, 241 and 245, 246, 247, 248, 249, 250, 251 and the like.

The content of the organic pigment (A) is preferably 40 to 80% by mass, more preferably 50 to 80% by mass, and 60 to 80% by mass in 100% by mass of the non-volatile content of the coloring composition from the viewpoint of thinning. More preferred.

(Miniaturization of organic pigments)
In the present invention, the organic pigment is preferably used in a finely divided form. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used. Among these, the salt milling treatment by the kneader method, which is one of the wet grinding methods, is preferable. The average primary particle size determined by the TEM (transmission electron microscope) of the finely divided pigment is preferably 5 to 90 nm. From the viewpoint of dispersibility and coloring power, the average primary particle size is more preferably 10 to 70 nm.

Salt milling is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. 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.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

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 amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

It is preferable to add a resin to the salt milling treatment from the viewpoint of coloring power and dispersion stability. The type of the resin is not particularly limited, and examples thereof include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. Among these, it is preferable that it is solid at room temperature, is insoluble in water, and is partially soluble in the above organic solvent. The amount of the resin used is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the organic pigment (A).

From the viewpoint of dispersion stability and coloring power, it is preferable to add the pigment derivative (B) to the salt milling treatment. The amount of the pigment derivative (B) used is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the organic pigment (A).

The organic pigment (A) can be used alone or in combination of two or more.

[Pigment derivative (B)]
(Pigment derivative (B1))
The pigment derivative (B) contains a pigment derivative (B1) represented by the general formula (1).

[In the general formula (1), one of R ₁ to R ₄ has a substituent represented by the general formula (2), and the other represents a hydrogen atom.
X represents —O— or —NH—, Y represents a divalent linking group containing an unsubstituted alkylene group, and _R5 to _R6 represent an unsubstituted alkyl group. ]

The alkyl groups in R5 to R6 in the general _formula ( ₂ ) are, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a dodecyl group. Group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldodecyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, Examples thereof include a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group and the like. Among these, a methyl group and an ethyl group are preferable from the viewpoint of dispersion stability.

Y in the general formula (2) is a divalent linking group containing an alkylene group which may have a substituent or an arylene group which may have a substituent. For example, the above-mentioned alkyl group and the above-mentioned alkyl group will be described later. A divalent linking group containing an alkylene group or an arylene group obtained by removing one hydrogen atom from the aryl group is preferable. The alkylene group or the arylene group can be linked to each other. Further, the alkylene group or the arylene group can be linked with a divalent linking group such as —O—, —COO−, —CO—, —OCO— and the like. Among these, an alkylene group having 2 to 4 carbon atoms and a phenylene group are preferable from the viewpoint of heat resistance and dye transfer.

X in the general formula (2) represents -O- or -NH-, and -NH- is preferable from the viewpoint of dispersion stability.

Specific examples of the pigment derivative (B1) represented by the general formula (1) (hereinafter, also referred to as the pigment derivative (B1)) are shown below. The present invention is not limited to these.

The content of the pigment derivative (B1) is preferably 5 to 30 parts by mass and 10 to 25 parts by mass with respect to 100 parts by mass of the organic pigment (A) from the viewpoint of viscosity, dispersion stability and suppression of foreign matter generation. Is more preferable.

The pigment derivative (B1) is preferably added in at least one of the above-mentioned pigment miniaturization step and the pigment dispersion treatment step described later, and more preferably in the pigment miniaturization step. When added in the process of miniaturizing the pigment, the coloring power is improved.

(Pigment derivative (B2))
As the pigment derivative (B), the pigment derivative (B2) represented by the following general formula (5) can be used in combination with the coloring composition from the viewpoint of viscosity, dispersion stability, and suppression of foreign matter generation.

General formula (5)

(In the general formula (5), R ¹ to R ⁹ each independently have a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 20 or less carbon atoms which may have a substituent, and a substituent. It represents an alkoxy group having 20 or less carbon atoms, or an aryl group having 20 or less carbon atoms which may have a substituent, and adjacent substituents are bonded to each other to form an aliphatic ring or an aromatic ring. It is also preferable that R ¹ to R ⁹ are independently hydrogen atoms or chlorine atoms, and R ⁶ to R ⁹ are chlorine atoms from the viewpoint of dispersion stability and suppression of foreign matter generation. Especially preferable.

Q represents a divalent linking group. A and B are independently represented by the following general formula (6), the following group represented by the general formula (7), —O— (CH ₂ ) _n −R ¹⁰ , —OR ¹¹ , -NR ¹² Represents a group selected from R ¹³ , -Cl, and -F, R ¹⁰ represents a optionally substituted nitrogen-containing heterocyclic residue, and R ¹¹ , R ¹² , and R ¹³ are hydrogen, respectively. The number of atoms may be an alkenyl group having 1 to 20 alkyl groups which may have a substituent and 2 to 20 carbon atoms which may have a substituent or the number of carbon atoms which may have a substituent. Represents an aryl group of 6 to 20, and n represents an integer of 0 to 20.

From the viewpoint of dispersion stability, A and B in the general formula (5) are preferably groups represented by the general formula (6) or the general formula (7), both of which are the general formula (6). It is preferably a group represented by, and more preferably the same group.

In the general formula (6), Y ¹ represents -NR ^20- or -O-, and Y ² may have a substituent and has an alkylene group having 1 to 20 carbon atoms and a substituent. It represents an alkenylene group having 2 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms which may have a substituent. These groups may be coupled to each other with a divalent linking group selected from -NR ^20- , -O-, -SO _2- , -CO-. R ²⁰ has a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. It represents an aryl group having 6 to 20 carbon atoms which may be used. R ¹⁴ and R ¹⁵ each represent an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent. R ¹⁴ and R ¹⁵ may be integrated to form a heterocyclic structure containing and substituted with additional nitrogen, oxygen or sulfur atoms.
In addition, Y ¹ is preferably ^−NR20− . R ²⁰ is preferably a hydrogen atom. Y ² is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of dispersion stability. From the viewpoint of dispersibility stability, R ¹⁴ and R ¹⁵ are preferably the same group, and the group is preferably an alkyl group having 1 to 6 carbon atoms.

In the general formula (7), Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR ^21- , -NR ²¹ -G-CO-, NR ²¹ -G-CONR ^22- , -NR ²¹ -G-SO. _2- , -NR ²¹ -G-SO ₂ NR ^22- , -OG-CO-, -OG-CONR ^21- , -OG-SO _2- , or -OG-SO ₂ NR ²¹ -represents. G may have an alkylene group having 1 to 20 carbon atoms which may have a substituent, and may have an alkaneylene group or a carbon which may have a substituent and may have 2 to 20 carbon atoms. Represents an arylene group having a number of 6 to 20. R ²¹ and R ²² each have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an alkenyl group. Represents an aryl group having 6 to 20 carbon atoms which may have a substituent. R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ each have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent. An alkenyl group of up to 20 or an aryl group having 6 to 20 carbon atoms which may have a substituent and R18 is an alkyl group having 1 to ²⁰ carbon atoms which may have a substituent. Alternatively, it represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent. ) G is synonymous with Y ² in the general formula (6), and the preferred range is also the same.

R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ in the general formula (7) have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent, respectively. It represents an alkenyl group having 2 to 20 carbon atoms which may be used, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and a hydrogen atom is preferable.

Q in the general formula (5) represents a divalent linking group, and is preferably a linking group represented by the following general formula (8).

General formula (8)

(In the general formula (8), q ¹ represents -NHSO _2- , -NHCO-, -OSO _2- , -OCO-, -NH-, or -O-.
q ² has an arylene group having 20 or less carbon atoms which may have a substituent, a heteroarylene group having 20 or less carbon atoms which may have a substituent, or 20 carbon atoms which may have a substituent. Representing the following alkylene group, when m is 2 or more, a plurality of q ^2s may be the same or different, and a plurality of q ^2s may be -NHSO _{2-, -NHCO-, -OSO 2 -} ,-. It may be linked by at least one divalent linking group selected from OCO-, -S-, -NH-, and -O-.
q ³ represents -NH- or -O-.
n represents an integer of 0 or 1, and m represents an integer of 0 to 5.

In the general formula (8), q ¹ is preferably -NHSO _2- or -OSO _2- , and q ² is preferably an arylene group having 20 or less carbon atoms or an alkylene group having 20 or less carbon atoms, and has 20 carbon atoms. The following arylene groups are more preferable, and phenylene groups are particularly preferable. For q ³ , -NH- is preferable. n and m are preferably 1.

Hereinafter, specific examples of the pigment derivative (B2) represented by the general formula (5) used in the present invention will be shown, but the present invention is not limited thereto.

The content of the pigment derivative (B2) is preferably 1 to 15 parts by mass and 2 to 10 parts by mass with respect to 100 parts by mass of the organic pigment (A) from the viewpoint of viscosity, dispersion stability and suppression of foreign matter generation. Is more preferable.

The pigment derivative (B) can be used alone or in combination of two or more.

The pigment derivative (B) can contain a pigment derivative (B1) and other pigment derivatives other than the pigment derivative (B2).

[Dispersed resin (C)]
The coloring composition in the present invention contains, as the dispersion resin (C), one or more of a phosphoric acid-based dispersion resin (C1) and a carboxylic acid-based dispersion resin (C2).

(Phosphoric acid-based dispersion resin (C1))
The phosphoric acid-based dispersion resin (C1) is a resin having a phosphoric acid bond [(—O) ₃ P = O] in the molecule. A preferred example is, for example, the phosphoric acid-based dispersion resin represented by either (C1-1) or (C1-2) below.

[Phosphoric acid-based dispersion resin (C1-1)]
The phosphoric acid-based dispersed resin (C1-1) is a resin represented by the following general formula (3).
(HO-) _3-n- PO- (OR ¹ ) _n General formula (3)
(In the general formula (3), R ¹ represents a polyester residue having a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)

Since the phosphoric acid-based dispersion resin represented by the general formula (3) has a large effect of suppressing the reaggregation of the pigment after dispersion, it is possible to produce a color filter having few foreign substances and excellent transparency.

The phosphoric acid-based dispersion resin represented by the general formula (3) is, for example, using monoalcohol as an initiator, ring-opening addition of a cyclic ester (first step), and then phosphoric acid esterification (second step). It is preferable to carry out the above.

The monoalcohol is a compound having one hydroxyl group in the molecule, and any of primary, secondary and tertiary alcohols can be used. Monoalcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol. , Cetyl alcohol, stearyl alcohol, oleyl alcohol, hexadecyl alcohol and the like. Among these, lauryl alcohol, N-hexanol, and hexadecyl alcohol are preferable.

In the first step, a polyester residue having a hydroxyl group at one end can be synthesized by ring-opening addition polymerization of a cyclic ester such as ε-caprolactone using monoalcohol as an initiator. The addition reaction of ε-caprolactone can be carried out by a known method, for example, a reactor to which a dehydration tube and a condenser are connected is charged with monoalcohol, ε-caprolactone, and a polymerization catalyst, and the reaction is carried out under a nitrogen stream. When a monoalcohol having a low boiling point is used, the reaction can be carried out under pressure using an autoclave. A solvent-free or suitable dehydrating solvent such as toluene or xylene can also be used for the reaction. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the product.

The reaction temperature in the first step is preferably 120 ° C to 220 ° C, more preferably 160 ° C to 210 ° C. When the reaction is carried out at an appropriate temperature, a reactant can be efficiently obtained while suppressing side reactions.
The number of moles of ε-caprolactone added to 1 mol of monoalcohol is preferably 1 to 50 mol, more preferably 3 to 20 mol. When the reaction is carried out at an appropriate ratio, a dispersed resin having an appropriate molecular weight can be obtained.

The polymerization catalyst is, for example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodine, tetrabutylammonium iodine, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium bromide. Tertiary ammonium salts such as, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium In addition to quaternary phosphonium salts such as iodine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, phosphorus compounds such as triphenylphosphine, and organic carboxylics such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate. In addition to alkali metal alcoholates such as acid salts, sodium ammoniums and potassium ammoniums, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride and the like can be mentioned.

As a second step, a polyester residue having a hydroxyl group at one end is reacted with a phosphoric acid esterifying agent such as phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, or phosphorus oxychloride to form a general formula ( The phosphoric acid-based dispersed resin represented by 2) can be obtained. Among these phosphoric acid esterifying agents, one or more phosphorus selected from the group consisting of orthophosphoric acid, polyphosphoric acid and phosphorus pentoxide because there is no by-product such as hydrochloric acid gas and no special equipment is required. Acid esterifying agents are preferred. Of these, polyphosphoric acid having an orthrinic acid equivalent content of 116% by mass is preferable.

The charging ratio of the phosphoric acid esterifying agent is preferably 0.5 to 1.5, preferably 1.0 to 1.5, as the molar ratio of phosphorus atoms in the phosphoric acid esterifying agent to the hydroxyl group of the polyester residue having a hydroxyl group at one end. It is more preferable than 3.3, and more preferably 1.05 to 1.2. When reacted at an appropriate ratio, a dispersed resin with few by-products can be obtained.

The reaction temperature in the second step is not particularly limited, but is preferably 40 ° C to 130 ° C, more preferably 50 ° C to 110 ° C, still more preferably 60 ° C to 100 ° C. When the reaction is carried out at an appropriate temperature, a dispersed resin having few unreacted substances and few by-products can be obtained.

From the viewpoint of dispersibility, the dispersion resin represented by the general formula (3) has a molar ratio of n = 1 phosphoric acid ester to n = 2 phosphoric acid ester of 100: 0 to 100:30. preferable.

Further, the dispersed resin represented by the general formula (3) preferably has a structure in which R ¹ is represented by the following general formula (3-1).
-(R ¹¹ -COO-) _m -R ¹² General formula (3-1)
(In the general formula (3-1), R ¹¹ represents a lactone residue, R ¹² represents a monoalcohol residue, and m represents an integer of 1 to 50.)
In the general formula (3-1), for example, when R ¹ is a polycaprolactone residue, pigment dispersibility and dry solubility are good, which is preferable. The number average molecular weight of the polycaprolactone residue is preferably 300 to 10,000.

[Phosphoric acid-based dispersion resin (C1-2)]
The phosphoric acid-based dispersion resin (C1-2) is a dispersion resin which is a copolymer of a phosphoric acid group-containing monomer and other monomers, and is, for example, JP-A-2003-253878, JP-A-2008. It is a resin described in Japanese Patent Publication No. 161737.

(Carboxylic acid-based dispersion resin (C2))
The carboxylic acid-based dispersion resin (C2) is a resin having a dispersion ability containing a carboxyl group (—COOH) in the molecule. A preferred example is the carboxylic acid-based dispersion resin represented by either (C2-1) or (C2-2) below.

[Carboxylic acid-based dispersion resin (C2-1)]
The carboxylic acid-based dispersion resin (C2-1) contains an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid dianhydride and tricarboxylic acid anhydride and a hydroxyl group in a hydroxyl group-containing compound. It is a resin containing a polyester moiety having a carboxyl group and a vinyl polymer moiety obtained by radically polymerizing a monomer, which are reacted.
First, the polyester portion will be described. The polyester portion is a site where a plurality of ester groups derived from the reaction between the acid anhydride group and the hydroxyl group are present.

The tetracarboxylic acid dianhydride is, for example, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1, 2,3,4-Cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetichydride, 3,5,6 -Tricarboxynorbornenan-2-acetate dianhydride, 2,3,4,5-tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride such as bicyclo [2.2.2] -Octo-7-en-2,3,5,6-tetracarboxylic acid dianhydride, Pyro Merit acid dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride , 3,3', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride , 3,3', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4' -Tetraphenylsilane Tetracarboxylic acid dianhydride, 1,2,3,4-frantetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'- Perfluoroisopropyridendiphthalic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalate) Acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4 '-Diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) ) Fluolene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] Fluolene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Examples thereof include succinic acid dianhydride or aromatic tetracarboxylic acid dianhydride such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride. Among these, aromatic tetracarboxylic acid dianhydride is preferable from the viewpoint of adsorptivity to pigments.

The tetracarboxylic acid dianhydride is not limited to the above-mentioned exemplified compound, and may have any structure as long as it has two acid anhydride groups. These may be used alone or in combination. Since the tetracarboxylic acid dianhydride forms a dispersed resin having two carboxyl groups in one unit of the tetracarboxylic acid dianhydride by the reaction with the hydroxyl group-containing compound, the dispersion of the present invention is made from the viewpoint of pigment adsorption. It is preferable as a component of the resin.

Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride and an aromatic tricarboxylic acid anhydride.

The aliphatic tricarboxylic acid anhydride is, for example, 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydrous, cis-propen-1,2,3-tricarboxylic acid-1. , 2-Ahydrogen, 1,3,4-cyclopentanetricarboxylic acid anhydride and the like.

The aromatic tricarboxylic acid is, for example, benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid. Anhydrous (1,2,4-naphthalentricarboxylic acid anhydride, 1,4,5-naphthalentricarboxylic acid anhydride, 2,3,6-naphthalentricarboxylic acid anhydride, 1,2,8-naphthalentricarboxylic acid anhydride) Etc.), 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2,3,2'- Examples thereof include biphenyl tricarboxylic acid anhydride, 3,4,4'-biphenylmethane tricarboxylic acid anhydride, 3,4,4'-biphenyl sulfonate tricarboxylic acid anhydride and the like. Among these, aromatic tricarboxylic acid anhydrides are preferable from the viewpoint of adsorptivity to pigments.

The molar ratio of the acid anhydride group in one or more acid anhydrides selected from the tetracarboxylic acid anhydride and the tricarboxylic acid anhydride and the hydroxyl group in the hydroxyl group-containing compound is acid anhydride group / hydroxyl group = 0.5 to. 1.5 is preferred. When the reaction is carried out at an appropriate ratio, it is easy to obtain a dispersed resin having good dispersibility.

The hydroxyl group-containing compound is preferably a polyol such as monool or a diol having a plurality of hydroxyl groups among the polyols. The hydroxyl group in the polyol functions as a bond starting point with the vinyl polymer moiety.
Examples of the polyol that serves as a bond starting point with the vinyl polymer portion include a compound having two hydroxyl groups and one thiol group in the molecule, and at least one hydroxyl group-containing compound selected from the group of one-terminal hydroxyl group-containing vinyl polymers. .. For example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2-mercapto-1, 2-Propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl -2-Methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like can be mentioned.

The carboxylic acid-based dispersion resin (C2-1) is more preferably the following carboxylic acid-based dispersion resin (C2-1-1) or (C2-1-2).

<< Carboxylic acid-based dispersion resin (C2-1-1) >>
The vinyl polymer moiety of the carboxylic acid-based dispersion resin (C2-1-1) is a single amount containing at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group. It is a dispersion resin containing a body unit and a carboxyl group-containing monomer unit.

(I-1) [Hydroxy group-containing monomer]
The hydroxyl group-containing monomer is a (meth) acrylate-based monomer having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4). -Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylates and cyclohexanedimethanol mono (meth) acrylates, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylates;
(Meta) acrylamide-based monomers with hydroxyl groups, such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) ) N- (hydroxyalkyl) (meth) acrylamide such as acrylamide;
A vinyl ether-based monomer having a hydroxyl group, for example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether;
An allyl ether-based monomer having a hydroxyl group, for example, a hydroxyalkylallyl such as 2-hydroxyethylallyl ether, 2- (or 3-) hydroxypropylallyl ether, 2-(or 3- or 4-) hydroxybutylallyl ether, etc. Ether is mentioned.

Further, a single amount obtained by adding an alkylene oxide and / or a lactone to the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkylallyl ether. The body is also preferable. As the alkylene oxide, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are preferable. When two or more kinds of alkylene oxides are used in combination, the binding form may be either random and / or block. As the lactone, for example, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more thereof are used. Both alkylene oxides and lactones may be added.

(I-2) [Oxetane group-containing monomer]
Examples of the oxetane group-containing monomer include (vinyloxyalkyl) alkyloxetane, (meth) acryloyloxyalkyl oxetane, and [(meth) acryloyloxyalkyl] alkyl oxetane. Of these, methyl methacrylate (3-ethyloxetane-3-yl) methyl and the like are preferable. Examples of commercially available products include ETERNALCOLL OXMA (methacrylic acid (3-ethyloxetane-3-yl) methyl) (manufactured by Ube Corporation).

(I-3) [t-butyl group-containing monomer]
Examples of the t-butyl group-containing monomer include t-butyl methacrylate and t-butyl acrylate.

(I-4) [Blocked Isocyanate Group-Containing Monomer]
Examples of the blocked isocyanate group-containing monomer include 2- (0- [1'-methylpropanolamino] carboxyamino) ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate and the like. .. Commercially available products include, for example, Karenz MOI-BM (2- (0- [1'-methylpropyridenamino] carboxyamino) ethyl methacrylate) (manufactured by Showa Denko KK), Karenz MOI-BP (2-[(3,3)). 5-Dimethylpyrazolyl) carbonylamino] ethylmethacrylate) (manufactured by Showa Denko KK) and the like.

The content of the thermally crosslinkable group-containing monomer unit is preferably 5 to 90% by mass, more preferably 20 to 60% by mass in all the monomers. If it is 5% by mass or more, a coloring composition having excellent resistance can be obtained due to the crosslinking effect, and if it is 90% by mass or less, the stability of the composition is improved.

(Ii) [Carboxyl group-containing monomer]
Examples of the carboxyl group-containing monomer include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid and the like. Among these, (meth) acrylic acid, which has good copolymerizability and is easily available, is preferable.

(Iii) [Other monomers]
Other monomers can be used for the vinyl polymer portion of the carboxylic acid-based dispersion resin (C2-1-1).
Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-. Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, and isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
N-substituted (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloyl morpholine, etc. Acrylamides;
Examples thereof include amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate; and nitriles such as (meth) acrylonitrile.

Examples thereof include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate. ..

<< Carboxylic acid-based dispersion resin (C2-1-2) >>
The carboxylic acid-based dispersion resin (C2-1-2) is a resin having a polymerizable unsaturated group in the vinyl polymer portion.
The method for producing a carboxylic acid-based dispersion resin (C2-1-2) is, for example, a reaction between a glycidyl methacrylate and a polymer having a hydroxyl group or a carboxyl group and a reactant, and a reaction between methacryloxyethyl isocyanate and a polymer having a hydroxyl group or a carboxyl group. Things etc. can be mentioned. Examples of the carboxylic acid-based dispersion resin (C2-1-2) include the dispersion resin described in JP-A-2011-157416.

[Carboxylic acid-based dispersion resin (C2-2)]
The carboxylic acid-based dispersion resin (C2-2) is a dispersion resin represented by the following general formula (4), and specifically, is a dispersion resin described in JP-A-2007-140487.
(HOOC-) _m -R ^2- (-COO- [-R ⁴ -COO-] _n -R ⁵ ) _t General formula (4)
(In the general formula (4), R ² is a tetravalent tetracarboxylic acid compound residue, R ⁵ is a monoalcohol residue, R ⁴ is a lactone residue, m is 2 or 3, and n is an integer of 1 to 50. , T represents (4-m).)

The content of the dispersed resin (C) is preferably 50 to 1000 parts by mass, preferably 80 to 800 parts by mass with respect to 100 parts by mass of the pigment derivative (B1) from the viewpoint of viscosity, dispersion stability, and suppression of foreign matter generation. Is more preferable.

(Basic dispersion resin (C3))
The coloring composition can further contain a basic dispersion resin (C3) from the viewpoint of dispersion stability. The basic dispersion resin (C3) is preferably, for example, a copolymer obtained by radically polymerizing a monomer containing a basic group-containing monomer. This dispersion resin has an affinity moiety containing a basic group adsorbed on a pigment. And stabilize the dispersion.

In the present invention, the basic group is a functional group having a nitrogen atom. The basic dispersion resin (C3) is, for example, a nitrogen atom-containing graft copolymer, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, pyridine, pyrimidine, or pyrazine on the side chain. Examples thereof include acrylic block copolymers having a nitrogen-containing heterocycle and the like, random copolymers, urethane resins and the like. Of these, block copolymers are more preferred.

In the present invention, from the viewpoint of dispersion stability, the basic group has at least one unit selected from the group represented by the following general formula (9), general formula (10), and general formula (11). Is preferable.

In the general formula (9), R ₁ to R ₃ represent a chain or cyclic hydrocarbon group which may have a hydrogen atom or a substituent independently of each other, and among R ₁ to R ₃ , Two or more may be bonded to each other to form a cyclic structure. R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.
R ₁ to R ₃ in the general formula (9) are, for example, an alkyl group having 1 to 4 carbon atoms which may have a substituent and an aralkyl group having 7 to 16 carbon atoms which may have a substituent. Is more preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group are particularly preferable.

In general formula (10), R ₅ and R ₆ represent chain or cyclic hydrocarbon groups that may have hydrogen atoms or substituents independently of each other, and are R ₅ and R ₆ . May combine with each other to form a cyclic structure. _R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.
For R ₅ and R ₆ in the general formula (10), for example, an alkyl group having 1 to 4 carbon atoms which may have a substituent is more preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are particularly preferable. preferable.

In the general formula (11), R ₇ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR ₁₂ . , R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R ₈ , R ₉ , R. ₁₀ , R ₁₁ independently represent a methyl group, an ethyl group, or a phenyl group, respectively. _R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.
In _R7 of the general formula (11), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched and cyclic alkyl groups. For example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group and the like can be mentioned.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. For example, a benzyl group, a phenethyl group, an α-methylbenzyl group, a 2-phenylpropane-2-yl group and the like can be mentioned.
Examples of the acyl group include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group. For example, an acetyl group, a benzoyl group and the like can be mentioned.
Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferable, a hydrogen atom and a methyl group are more preferable, and a methyl group is further preferable.

In the general formulas (9), (10), and (11), the divalent linking group X is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R _13- , -COO. -R _14- (However, R ₁₃ and R ₁₄ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)) and the like. Be done. Of these, -COO-R ₁₄ -is preferable. Further, in the above formula (9), examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO _4- , BF _4- ^, CH ₃ COO ⁻ , PF ₆ ^{− and} the like.

The quaternary ammonium base-containing monomer forming the general formula (9) is, for example, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride. , (Meta) acryloyloxyethyl methylmorpholinoammonium chloride and other alkyl (meth) acrylate-based quaternary ammonium salts, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylamino Examples thereof include alkyl (meth) acryloylamide-based quaternary ammonium salts such as ethyldimethylbenzylammonium chloride, dimethyldiallylammoniummethylsulfate, and trimethylvinylphenylammonium chloride.

The tertiary amine group-containing monomer forming the general formula (10) is, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl. (Meta) acrylates having a tertiary amino group such as (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate;
Tertiary such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. (Meta) acrylamides with amino groups;
And so on.

Examples of the monomer forming the general formula (11) include compounds represented by the following general formulas (11-1) to (11-11).

In the general formulas (11-1) to (11-11), R ₄ represents hydrogen or a methyl group.

Of these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R ₄ is a methyl group in the above general formula (11-1)), 1,2,2,6,6-pentamethylpiperidyl Methacrylate (a compound in which R ₄ is a methyl group in the above general formula (11-2)) is preferable, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferable.

The amine value of the basic dispersion resin (C3) is preferably 50 to 180 mgKOH / g.

For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate. , Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate , Linear or branched alkyl (meth) acrylates such as isomiristyl (meth) acrylates, stearyl (meth) acrylates, and isostearyl (meth) acrylates;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meta) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meta) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate , Diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, Triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene (Poly) alkylene glycol monoalkyl ether (meth) acrylates such as glycol monolauryl ether (meth) acrylates, polyethylene glycol monostearyl ether (meth) acrylates, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylates;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) (meth). ) (Poly) alkylene glycol (meth) acrylates having an aromatic ring such as acrylate;
Alkyloxy such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meta) acrylates having a silyl group;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethyl Siloxane (silicone macromer);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin; In addition, nitriles such as (meth) acrylonitrile may be mentioned.
In addition, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acids such as vinyl acetate and vinyl propionate. Examples include vinyls.

Further, a carboxyl group-containing monomer can also be used in combination. Carboxyl group-containing monomers include, for example, (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth). ) Acryloyloxypropylphthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropylhexahydrophthalate, β-carboxyethyl (meth) acrylate, and ω-carboxypolycaprolactone (meth) ) Examples include acrylate.

Further, an amino group-containing monomer other than the units represented by the general formulas (9), (10) and (11) may be used in combination as long as the effect of the present invention is not impaired.

The basic dispersion resin (C3) can be used by forming a salt with an acidic compound.
Examples of the acidic compound include a phosphoric acid compound and a sulfonic acid compound.

Examples of the phosphoric acid compound include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphate, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate and the like.
Examples of the sulfonic acid compound include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfate, monoethylsulfate, monon-propylsulfate and the like. A hydrate such as p-toluenesulfonic acid monohydrate may be used.
Among these, a phosphoric acid compound is preferable in terms of suppressing foreign substances.

The molecular weight of the basic dispersion resin (C3) is preferably 1,000 to 100,000 on a polystyrene-equivalent weight average from the viewpoint of dispersion stability.

The content of the basic dispersion resin (C3) is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the organic pigment (A) from the viewpoint of dispersion stability.

[Binder resin (D)]
The coloring composition in the present invention preferably contains the binder resin (D) from the viewpoints of film forming property, coating film resistance, developability, and pattern forming property.

The binder resin (D) is preferably a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm when a film having a thickness of 2 μm is formed. The transmittance is more preferably 95% or more. The binder resin (D) is preferably a thermoplastic resin or an active energy ray-curable resin when classified according to its main curing method. The active energy ray-curable resin preferably has a thermosetting functional group. Further, the binder resin (D) is preferably an alkali-soluble resin from the viewpoint of developability. The binder resin (D) can be used alone or in combination of two or more.

The content of the binder resin (D) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the organic pigment (A) from the viewpoint of film forming property and coating film resistance. ..

(Thermoplastic resin)
The thermoplastic resin is, for example, an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, a polyurethane resin, and the like. Examples thereof include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
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. The alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene /. (Anhydrous) maleic anhydride 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)
As the binder resin (D), an alkali-soluble resin having a polymerizable unsaturated group is particularly preferable from the viewpoint of coating film resistance. In particular, by using a resin having a polymerizable unsaturated group introduced by the methods (i) and (ii) shown below, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. Increases the crosslink density and improves the coating resistance.

(Method (i))
Method (i) is a monocarboxylic acid having a polymerizable unsaturated group in the side chain epoxy group of the copolymer obtained by copolymerizing, for example, an epoxy group-containing monomer and another monomer. There is a method of adding a carboxyl group of a monomer and further reacting the generated hydroxyl group with a polybasic acid anhydride to introduce a polymerizable unsaturated group and a carboxyl group.

Epoxy group-containing monomers include, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, and 3,4-. Epoxycyclohexyl (meth) acrylate can be mentioned. Among these, glycidyl (meth) acrylate is preferable from the viewpoint of reactivity with the monocarboxylic acid monomer in the next step.

The monocarboxylic acid monomer is, for example, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted compound. Such as monocarboxylic acid and the like.

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 a polymerizable unsaturated group is used as the polybasic acid anhydride, the polymerizable unsaturated group can be further increased.

As a method similar to the method (i), for example, a part of the side chain carboxyl group of the copolymer obtained by copolymerizing a monocarboxylic acid monomer with one or more other types of monomers. There is a method of introducing a polymerizable unsaturated group and a carboxyl group by subjecting an epoxy group-containing monomer to an addition reaction.

(Method (ii))
As the method (ii), a hydroxyl group-containing monomer is used, and the side chain hydroxyl group of the copolymer obtained by copolymerizing with the monomer of the monocarboxylic acid monomer or other monomers is used. , There is a method of reacting the isocyanate group of the isocyanate group-containing monomer.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth). Examples thereof include hydroxyalkyl methacrylates such as acrylates and cyclohexanedimethanol mono (meth) acrylates. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with an ethylene oxide, a propylene oxide, and / or a butylene oxide, a poly γ-valerolactone, a 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 isocyanate group-containing monomer include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, and 1,1-bis [methacryloyloxy] ethyl isocyanate.

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 or styrenes such as α-methyl styrene, 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 Hexanoart, N-substituted maleimides such as N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimideacridin, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethyleneoxide (EO) -modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (meth) acrylate of paracumylphenol, EO-modified (meth) acrylate of nonylphenol, PO-modified (meth) acrylate of nonylphenol, etc. Can be mentioned.

Further, a carboxyl group-containing monomer can be used. Examples of the carboxyl group-containing 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 monomer can be used. The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexanedimethanol mono. Examples thereof include hydroxyalkyl (meth) acrylates such as (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 monomer can also be mentioned. The phosphoric acid ester group-containing monomer can be, for example, a monomer obtained by reacting the hydroxyl group of the hydroxyl group-containing monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

The monomer used for the synthesis of the binder resin (D) may be used alone or in combination of two or more.

As the binder resin (D), an alkali-soluble resin having a polymerizable unsaturated group and an alkali-soluble resin having no polymerizable unsaturated group can be used in combination in order to adjust the degree of curing of the coating film.

The weight average molecular weight (Mw) of the binder resin (D) is 2,000 or more and 40,000 or less, preferably 3,000 or more and 3,000 or less, and 4,000 or more and 20, from the viewpoint of alkali development solubility. More preferably, it is 000 or less. Further, the value of Mw / Mn is preferably 10 or less. The appropriate weight average molecular weight (Mw) improves the adhesion to the substrate and improves the alkali development solubility.

The acid value of the binder resin (D) is preferably 50 or more and 200 or less (mgKOH / g), more preferably 70 or more and 180 or less, and further preferably 90 or more and 170 or less in order to impart alkali development solubility. Alkaline development solubility is improved by an appropriate acid value, the residue is small, the linearity of the pattern is improved, and the adhesion to the substrate is improved.

The binder resin (D) can be used alone or in combination of two or more.

(Thermosetting compound (G))
The coloring composition of the present invention can further contain a thermosetting compound (G). By containing the thermosetting compound, when the color filter is produced, it reacts at the time of firing the filter segment and the crosslink density of the coating film is improved. As a result, heat resistance is improved, pigment aggregation during firing is suppressed, and coloring power is improved.

The thermosetting compound (G) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferable.

[Epoxy compound (G-1)]
Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted Dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones. Polycondensate with (acemonate, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyldimethanol , Α, α, α', α'-biphenyldimethanol, etc.), and phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) , Polycondensate of bisphenols and various aldehydes, glycidyl ether-based epoxy resin obtained by glycidylizing alcohols, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine-based epoxy resin, glycidyl ester-based Examples include epoxy resin.

Commercially available products include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (the above are trade names; manufactured by Yuka Shell Epoxy), Epicoat 1004, and Epicoat 1256 (the above are trade names). ; Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (Product Name; Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (Product Name; Nippon Kayaku Co., Ltd.), JER 1032H60 (Product Name; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (trade name; manufactured by Nippon Kayaku), EPPN-201 (trade name; manufactured by Nippon Kayaku), JER152, JER154 (trade name; manufactured by Japan Epoxy Resin), EOCN-102S, EOCN- 103S, EOCN-104S, EOCN-1020 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (trade name; manufactured by Daicel Chemical Industry Co., Ltd.), Denacol EX-211, 212, 252, 313 , 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, (the above are trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC- S (manufactured by Nissan Chemical Industry Co., Ltd.) and the like can be mentioned.

The content of the epoxy compound is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the organic pigment (A). When an appropriate amount is added, the coloring power and heat resistance are improved.

[Oxetane compound (G-2)]
The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include a monofunctional oxetane compound, a bifunctional oxetane compound, and a trifunctional or higher functional oxetane compound.
The monofunctional oxetane compound is, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methylmethacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-. (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxy) Cyril) propoxy] methyl} oxetane and the like.
Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

Bifunctional oxetane compounds include, for example, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 1,4-Bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl ether- 3-Ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-Ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycolbis (3) -Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-) Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like can be mentioned.
Specific examples include OXBP and OXTP manufactured by Ube Kosan Co., Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

Examples of the trifunctional or higher functional oxetane compound include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl-3). -Oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-) 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaxe (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing oxetane group (eg) , Oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462) and polymers obtained by radically polymerizing (meth) acrylic monomers such as the above-mentioned OXE-30.

The content of the oxetane compound is usually 0.5 to 50 parts by mass, preferably 1 to 40 parts by mass in 100 parts by mass of the non-volatile content of the coloring composition. When the content of the oxetane compound is within the above range, it is preferable because an excellent coating film having good water stains and high chemical resistance can be obtained.

The melamine compound refers to a compound having a melamine ring structure. The melamine compound is preferably a methylol type or an ether type, and more preferably a melamine compound having an average number of methylol groups and / or ether groups of 5.0 or more per melamine ring. When an appropriate amount of the melamine compound is used, the coloring power is improved and the resistance to N-methylpyrrolidone is also improved.

Commercially available products include, for example, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS- 001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 ( Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Japan Cytec Industries) and the like.

Among these, the number of methylol groups and / or ether groups per melamine ring is 5.0 or more on average, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30. , MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.) Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries) Etc. are preferable in terms of increasing the crosslink density.

The thermosetting compound (G) can be used alone or in combination of two or more.

(Hardener)
In order to assist the curing of the thermosetting compound (G), the coloring composition of the present invention may be used in combination with a curing agent (curing accelerator), if necessary. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. The curing agent is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2). -Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4 -Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- Examples thereof include S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.).

The curing agent can be used alone or in combination of two or more.

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (G).

[Organic solvent (P)]
The coloring composition of the present invention can contain an organic solvent (P).
The organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol di. Acetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3- Ethyl 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-propylacetate, 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 monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoterriary 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, diisobutyl ketone, 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, cyclohexanolacetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, zip Lopyrene 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 Examples thereof include isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. Among these, glycols such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are considered from the viewpoint of dispersibility of organic pigments and solubility of binder resin. Alcohols such as acetates, benzyl alcohols and diacetone alcohols and ketones such as cyclohexanone are preferable.

The organic solvent (P) can be used alone or in combination of two or more.

From the viewpoint of coatability, the coloring composition of the present invention preferably has a viscosity at 25 ° C. of less than 50 mPa · S, more preferably less than 15 mPa · S, and even more preferably 10 mPa · S or less. The viscosity can be adjusted by blending an organic solvent (P) or the like.

<Photosensitive coloring composition>
The photosensitive coloring composition of the present invention contains a coloring composition, a polymerizable compound (E), and a photopolymerizable initiator (F).

[Polymerizable compound (E)]
The polymerizable compound (E) is a monomer (monomer) or an oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (E) include an acid group-containing monomer, a urethane bond-containing monomer, and other monomers.

Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.
The acid group-containing monomer is, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyhydric carboxylic acid and a monohydroxyalkyl (meth). ) Examples thereof include esterified products with acrylates. Specific examples include monohydroxyoligoacrylates such as trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. , Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxy Examples thereof include monohydroxymonoacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

(Urethane bond-containing monomer)
The urethane bond-containing monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a (meth) acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further having a hydroxyl group. Examples thereof include polyfunctional urethane acrylate obtained by reaction.

The (meth) acrylate having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate methacrylate , Gloxydimethacrylate, 2-hydroxy-3-acryloylpropylmethacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, a hydroxyl group-containing polyol polyacrylate and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate and the like.

Other monomers include, for example, methyl (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, Polypropylene glycol di (meth) acrylate, Trimethylol propanthry (meth) acrylate, Phenoxy Tetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, isocianul Acid EO modified tri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (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 (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, methylol Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, and urethane acrylate of melamine and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta. Examples thereof include erythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

Examples of commercially available products of the polymerizable compound (E) include Aronix M309, M321, M350, M315, M305, M450, M408, M400, M402, M510, and M520 manufactured by Toagosei Corporation.

The polymerizable compound (E) can be used alone or in combination of two or more.

The content of the polymerizable compound (E) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is blended, photocurability and developability are improved.

[Photopolymerization Initiator (F)]
The photopolymerization initiator (F) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-. On, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) ) Phenyl] -2- (phenylmethyl) -1-butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Acetphenone compounds such as butanone; 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, Benzophenone compounds such as acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2 -Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloro). Methyl) -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) Triazine compounds such as -6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) phenyl- , 2- (O-benzoyloxime)], or etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime), etc. Oxym ester compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrene quinone, camphorquinone , Ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanosen compounds.

Commercially available products include "Omnirad 907" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one) and "Omnirad 369E" (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one) manufactured by IGM Resins as acetphenone compounds. 2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (phenylmethyl) -1-butanone), "Omnirad 379EG" (2- (dimethylamino) -2-[(4-4-) Methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), as a phosphine compound, manufactured by IGM Resins, "Omnirad 819" (bis (2,4,6-trimethylbenzoyl)) -Phenylphosphinoxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphinoxide), and the like. Among these, it is preferable to contain an oxime ester compound.

(Oxime ester compound)
The oxime ester compound breaks the NO bond of the oxime by absorbing ultraviolet rays, and produces iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the organic pigment concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low, but the oxime ester compound is preferably used because it has high quantum efficiency. Ru.

Commercially available products include, for example, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01), etanone, 1- [9-ethyl-6. -(2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02), IRGACURE OXE 04 (all manufactured by BASF Japan), N-1919, NCI- 831, NCI-930 (all manufactured by ADEKA), TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-345 (all manufactured by Changzhou Strong New Materials Co., Ltd.) And so on. Further, the oxime ester-based photopolymerization described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-02998, etc. Initiators can also be mentioned.

The photopolymerization initiator (F) can be used alone or in combination of two or more.

The content of the photopolymerization initiator (F) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, with respect to 100 parts by mass of the organic pigment (A) from the viewpoint of photocurability and developability. preferable. When an appropriate amount is contained, the adhesion between the substrate and the pattern is improved, and the brightness of the post-bak is less likely to decrease.

[Sensitizer (H)]
The photosensitive coloring composition of the present invention can contain a sensitizer (H).
The sensitizer (H) is, for example, a chalcone derivative, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivative represented by benzyl, camphorquinone, etc., benzoin derivative, fluorene derivative, naphthoquinone. Polymethine dyes such as derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, aclysine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin. Derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphy Radin derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, anuren derivative, spiropyrane derivative, spiroxazine derivative, thiospiropyrane derivative, metal arene complex, organic ruthenium complex, or Michiller ketone derivative, α-a Syroxyester, acyloxide, methylphenylglycilate, benzyl, 9,10-phenanslenquinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone.

Of these, thioxanthone derivatives, Mihiler ketone derivatives, and carbazole derivatives are preferable, with 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxy. Thioxanthone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethyl Carbazole, 3,6-dibenzoyl-N-ethylcarbazole and the like are more preferable.

The sensitizer (H) can be used alone or in combination of two or more.

Examples of commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis (diethylamino) benzophenone manufactured by Chemark Chemical Co., Ltd.). ..

The content of the sensitizer (H) is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (F) from the viewpoint of photocurability and developability. ..

[Thiol chain transfer agent (I)]
The photosensitive coloring composition can contain a thiol-based chain transfer agent (I). When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, chiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the sensitivity of the photosensitive coloring composition is improved.

The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, it becomes easier to photo-cure from the surface of the film to the deepest part.

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylolpropane Tristhioglycolate, Trimethylolpropane Tristhiopropionate, Trimethylolpropanetris (3-mercaptobutyrate), Pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, Tristrimercaptopropionate (2-Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine And the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate and the like.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the light sensitivity and the tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating film.

[Polymerization inhibitor (J)]
The photosensitive coloring composition may contain a polymerization inhibitor (J). This prevents exposure to the diffracted light of the mask during exposure by the photolithography method, and makes it easier to obtain a good pattern shape.
The polymerization inhibitor (J) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, Alkyl catechol compounds such as 4-t-butyl catechol, 3,5-di-t-butyl catechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4 Alkyl resorcinol compounds such as -propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butyl Alkylhydroquinone compounds such as hydroquinone and 2,5-di-t-butylhydroquinone, phosphinic compounds such as tributylphosphin, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine. Examples thereof include phosphine oxide compounds such as oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, fluoroglucolcin and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, it becomes easy to obtain a good pattern shape.

[Ultraviolet absorber (K)]
The photosensitive coloring composition can contain an ultraviolet absorber (K). The ultraviolet absorber (K) is an organic compound having an ultraviolet absorbing function, and is a benzotriazole-based organic compound, a triazine-based organic compound, a benzophenone-based organic compound, a salicylic acid ester-based organic compound, a cyanoacrylate-based organic compound, and a salicylate-based organic compound. Examples include compounds.

Benzotriazole compounds include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3. , 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole 2-yl)-(1, Mix of 1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester, 2- (2H-benzotriazole 2-yl) -4,6-bis (1-methyl-1-phenylethyl) Phenol, 2- (2H-benzotriazole 2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (3-) Reaction product of (2H-benzotriazole 2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole 2-yl) -4- (1,1,1) 3,3-Tetramethylbutyl) Phenol, 2,2'-Methylenebis [6- (2H-benzotriazole2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- ( 2H-benzotriazole 2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole 2-yl) -6-t-butyl-4-methylphenol, 2- (3,5-di-t) -Amil-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-5- [2- (methacryloyloxy) ethyl] phenyl] -2H-benzotriazole, octyl-3- [3-tert-butyl-4- Hydroxy-5- (5-chloro-2H-benzotriazole 2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole 2) -Il) Phenol] Propionate can be mentioned.

Commercially available products are BASF Japan's TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130, ADEKA's ADEKA STAB LA-29, LA-31RG, LA-32, LA. -36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

The triazine compounds include, for example, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4. 6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4 -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-( Hexyloxy) Phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6- Examples thereof include tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

Examples of commercially available products include KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, ADEKA Adecaster LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical Co., Ltd. Be done.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-. Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade Examples thereof include syroxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of commercially available products include KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Sipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd. and the like.

Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate.

The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, it becomes easy to obtain a good pattern shape. When the sensitizer (H) is contained, the content of the photopolymerization initiator (F) includes the content of the sensitizer (H).

The total content of the photopolymerization initiator (F) and the ultraviolet absorber (K) is preferably 1 to 20% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. By containing an appropriate amount, it is easy to achieve both adhesion to the substrate and resolution. When the sensitizer (H) is contained, the content of the photopolymerization initiator (F) includes the content of the sensitizer (H).

[Antioxidant (L)]
The photosensitive coloring composition may contain an antioxidant (L). As the antioxidant, the photopolymerization initiator and the thermosetting compound contained in the photosensitive coloring composition prevent yellowing due to oxidation by the heat curing and the heat process at the time of ITO annealing, and reduce the transmittance of the film. Can be suppressed. In particular, when the concentration of the organic pigment in the photosensitive coloring composition is high, the content of the photopolymerizable compound (E) is relatively reduced. Is easy to yellow. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and suppress a decrease in the transmittance of the coating film.

Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present specification, the antioxidant is preferably a compound containing no halogen atom.
Among these, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable from the viewpoint of achieving both the transmittance and the sensitivity of the coating film.

The hindered phenolic antioxidant is, for example, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H). , 3H, 5H) -trion, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 4,4'-butylidene-bis- (2- t-butyl-5-methylphenol), 3- (3,5-di-t-butyl-4-hydroxyphenyl) stearyl propionate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8 , 10-Tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1,3 , 5-Tris (3-hydroxy-4-t-butyl-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2' -Methylbis (6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis (Dodecylthiomethyl) -o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis (octylthiomethyl) -o-cresol, bis [ 3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis [3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis- (4, 4, 6-dimethyl-phenol), 2,2'-methylene-bis- (6- (1-methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, etc. Can be mentioned.

Commercially available products are ADEKA's ADEKA STUB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330, Chemipro's KEMINOX 101, 179, 76, 9425, BASF Japan. Examples thereof include IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, and Sianox CY-1790 and CY-2777 manufactured by Sun Chemical.

Hindered amine antioxidants include, for example, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6). -Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6) -Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-Tetramethyl-4-piperidylmethacrylate, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine , Poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) ) Imino] -hexamethylene- [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol and 3, Ester of 5,5-trimethylhexanoic acid, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl)) Amino} -1,3,5-triazin-2-yl] -4,7-diazadecan-1,10-diamine, bisdecanediate (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,5-bis) 1 dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate methyl 1,2,2,6,6-pentamethyl-4-piperidylsevakate, poly [[6-morpholino-s-triazine-2,4 -Diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl) imino]], 2, 2,6,6-Tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, 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 And so on.

Commercially available products are ADEKA's ADEKA STUB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA- 402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin249 manufactured by BASF Japan, TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3329, UV-3385 manufactured by Sun Chemical Co., Ltd. And so on.

Phylline antioxidants include, for example, di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis (4,6). -Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4' -Isopropyridene diphenyl diphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisodecylphosphite, tris (isodecyl) phosphite, triphenylphosphite, tetrakis (2,4-di-t-butylphenyl)- 4,4-Biphenyldiphoshonito, Tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropyridene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (biphenyl) phosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (Nonylphenyl) 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, sodiumbis (4-t-butylphenyl) phos Fight, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2,4) -Dit-butyl-6-methylphenyl) and the like.

Examples of commercially available products include ADEKA's ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP, BASF Japan's IRGAFOS168, and Clariant Chemicals' HostanoxP-EPQ. Be done.

Sulfur-based antioxidants include, for example, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (dodecylthio) propionate], 3,3'-. Ditridecyl thiobispropionate, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl] -o- Cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like can be mentioned.

Examples of commercially available products include ADEKA Stab AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

The antioxidant (L) can be used alone or in combination of two or more.

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. Appropriate amounts improve transmittance, spectral characteristics, and sensitivity.

[Leveling agent (M)]
The photosensitive coloring composition may contain a leveling agent. As a result, the wettability to the substrate and the dryness of the film at the time of film formation are further improved. Examples of the leveling agent include a silicone-based surfactant, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant and the like.

The leveling agent (M) can be used alone or in combination of two or more.

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. Within this range, the balance between the coatability of the photosensitive coloring composition, the pattern adhesion, and the transmittance is further improved.

[Storage stabilizer (N)]
The photosensitive coloring composition may contain a storage stabilizer to stabilize the viscosity of the composition over time. The storage stabilizer (N) includes, for example, quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenyl and the like. Examples thereof include organic phosphine and phosphite. The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the organic pigment (A).

[Adhesion improver (O)]
The photosensitive coloring composition may contain an adhesion improver. This further improves the adhesion between the coating film and the base material. In addition, the photolithography method facilitates the formation of narrow patterns. Examples of the adhesion improver include a silane coupling agent and the like.

The adhesion improver (O) is, for example, vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxy. (Meta) acrylic silanes such as silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxysilanes such as dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3- Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, Aminosilanes such as 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3- Mercapts such as mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide Examples thereof include silane coupling agents such as sulfides such as, and isocyanates such as 3-isocyanuspropyltriethoxysilane.

The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the organic pigment (A). When an appropriate amount is contained, the light sensitivity of the photosensitive coloring composition is improved, the adhesion of the coating film is further improved, and the resolution of the pattern is further improved.

<Manufacturing method of coloring composition>
The method for producing a coloring composition of the present invention is to mix an organic pigment (A), a pigment derivative (B1), a dispersion resin (C), and a binder resin (D), and use a two-roll mill, a three-roll mill, a ball mill, and a horizontal type. It can be dispersed and manufactured by using various dispersion means such as a sand mill, a vertical sand mill, an annular bead mill, or an attritor. When two or more kinds of organic pigments (A) are used, they can be dispersed separately. In addition, the organic pigment (A) and the pigment derivative (B1) can be used in advance for miniaturization treatment and dispersion treatment.

The average dispersed particle size (secondary particle size) of the organic pigment (A) in the coloring composition of the present invention is preferably 30 to 200 nm, more preferably 40 to 200 nm. Within this range, a photosensitive coloring composition having high dispersion stability can be obtained.

As a method for measuring the average dispersed particle size (secondary particle size), for example, a Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method), is used, and particle permeability is absorbed in an absorption mode. The shape may be non-spherical and D50 may be the average diameter. As the diluting solvent for measurement, the organic solvent used for dispersion is used, and it is preferable to measure the sample treated by ultrasonic waves immediately after sample preparation because it is easy to obtain results with little variation.

<Manufacturing method of photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be prepared by mixing the coloring composition, the polymerizable compound (E), and the photopolymerization initiator (F).

The coloring composition and the photosensitive coloring composition of the present invention have coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove coarse particles of 5.5 μm or more and 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. More preferably, it is 0.3 μm or less.

The content of the organic pigment (A) in the photosensitive coloring composition of the present invention is preferably 40 to 80% by mass, more preferably 50 to 80% by mass, based on 100% by mass of the total non-volatile content, from the viewpoint of thinning. 60 to 80% by mass is particularly preferable.

From the viewpoint of coatability, the photosensitive coloring composition preferably has a viscosity at 25 ° C. of less than 50 mPa · S, more preferably less than 15 mPa · S, and particularly preferably 10 mPa · S or less.

<Color filter>
The color filter of the present invention comprises a substrate and a filter segment formed from a photosensitive coloring composition. The color filter segment preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of organic pigment to be used. Further, the color filter may have a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment in place of or in addition to the color filter segment. A green filter segment can be prepared from the photosensitive coloring composition of the present invention.
Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate that uses an aluminum electrode or a metal thin film as a reflective surface.

[Manufacturing method of color filter]
The color filter of the present invention has a step of applying the photosensitive coloring composition of the present invention on a substrate to form a colored layer, a step of exposing the colored layer in a pattern through a mask, and an unexposed portion. Can be obtained by a step of developing and removing and forming a colored pattern.
Further, if necessary, a step of drying the colored layer (pre-baking step) and a step of thermosetting the colored pattern (post-baking) may be provided.

Hereinafter, the method for manufacturing the color filter of the present invention will be described in detail.

(Step of forming a colored layer)
In the step of forming the colored layer, the photosensitive coloring composition of the present invention is coated on a substrate by rotary coating, roll coating, slit coating, casting coating, inkjet coating, or the like, and if necessary. Dry (pre-bake) at a temperature of 50 to 120 ° C. for 10 to 120 seconds using an oven, a hot plate, or the like.
Examples of the substrate include a glass substrate and a substrate on which an image pickup element such as a CCD or CMOS is provided on a silicon substrate. An undercoat layer may be provided on the substrate, if necessary.

(Process of exposure in a pattern)
In the exposure step, the colored layer is exposed to a specific pattern via a mask using an exposure device such as a stepper. This gives a cured film.
For the exposure, for example, ultraviolet rays such as g-line, h-line, and i-line are preferably used.

The film thickness of the cured film is preferably 1.0 μm or less, more preferably 0.2 to 0.8 μm, and particularly preferably 0.2 to 0.6 μm.

(Development process)
By performing the alkaline development treatment, the colored layer of the unirradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the cured portion remains.
The developing solution is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc. Pyrrole, piperidine, 1,8-diazabicyclo-[5. 4. 0] -7-Alkaline compounds such as undecene can be mentioned. The concentration of the developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When the alkali concentration is within the above range, roughening and peeling of the pattern can be more effectively suppressed, and the residual film ratio can be further improved. In addition, the decrease in development speed and the generation of development residue can be further suppressed.

The developing method includes, for example, a dip method, a spray method, a paddle method and the like, and the temperature is preferably 15 to 40 ° C. After alkaline development, it is preferable to wash with pure water.

Then, after drying, it is preferable to perform heat treatment (post-baking) in order to sufficiently cure the cured film. The heating temperature of the post bake is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

The color filter of the present invention can be suitably used for a solid-state image sensor such as a CCD or CMOS, and is particularly suitable for a high-resolution CCD or CMOS having more than 1 million pixels. The color filter of the present invention can be used, for example, as a color filter arranged between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

<Solid image sensor>
The solid-state image sensor of the present invention includes the above color filter. The solid-state image sensor of the present invention has, for example, the following configurations.

A transfer electrode made of a plurality of photodiodes and polysilicon or the like constituting a light receiving area of a solid-state image sensor (CDCD image sensor, CMOS image sensor, etc.) is provided on a substrate, and a photo is taken on the photodiode and the transfer electrode. The device has a light-shielding film made of tungsten or the like in which only the light-receiving part of the diode is opened, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. It is a configuration having the color filter of the present invention on the protective film.
Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective layer under the color filter (the side closer to the substrate), or a configuration having a condensing means on the color filter. And so on.

The color filter of the present invention can be used not only for the solid-state image sensor but also for an image display device such as a liquid crystal display device or an organic EL display device. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image having a good hue of the displayed image and excellent display characteristics.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these. In addition, "part" is "mass part", and "%" is "mass%".

Prior to the embodiment, each measurement method will be described.

The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and (mgKOH / g) of the resin are as follows.

(Average molecular weight of dispersed resin and binder resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the dispersed resin and the binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Co., Ltd.) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40 ° C. , Tetrahydrofuran (THF) solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in 20 microliters. The molecular weight is a polystyrene-equivalent value.

(Acid value of dispersed resin and binder resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the dispersion resin and binder resin solution, stir to dissolve them uniformly, and use a 0.1 mol / L KOH aqueous solution as a titration solution as an automatic titrator (“COM-”. 555 ”manufactured by Hiranuma Sangyo Co., Ltd.) was used for titration, and the acid value (mgKOH / g) was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

(Amine value of basic dispersion resin)
The amine value of the basic dispersion resin is a value obtained by converting the measured total (mgKOH / g) into a non-volatile component according to the method of ASTM D 2074.

<Production example of phthalocyanine green pigment (A2)>
(Miniaturized phthalocyanine green pigment (A2-1))
C. I. 200 parts of Pigment Green 36 (Rionol Green 6YK manufactured by Toyo Color Co., Ltd.), 1,400 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 a finely divided phthalocyanine green pigment (A2-1) was obtained.

(Miniaturized phthalocyanine green pigment (A2-2))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC Corporation), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is put into 3,000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 97 parts of finely divided phthalocyanine green pigment (A2-2) was obtained.

(Miniaturized phthalocyanine green pigment (A2-3))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine. The temperature was raised to 130 ° C. over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of crushed sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-armed kneader and kneaded at 100 ° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a finely divided phthalocyanine green pigment (A2-3). The obtained finely divided phthalocyanine green pigment (A1-3) has an average of 12.71 halogen atoms in one molecule from fluorescent X-ray analysis, of which an average of 10.22 bromine atoms and chlorine. The average number of atoms was 2.49.

(Miniaturized phthalocyanine green pigment (A2-4))
According to the examples of JP-A-2017-11138, a finely divided phthalocyanine green pigment (A2-4) represented by the following chemical formula 1 was obtained. The structure is shown below.
Chemical formula (1)

(Miniaturized phthalocyanine green pigment (A2-5))
A finely divided phthalocyanine green pigment (A2-5) represented by the following chemical formula 2 was obtained according to an example of JP-A-2017-11138. The structure is shown below.
Chemical formula (2)

<Production example of the pigment derivative (B1) represented by the general formula (1)>
(Pigment derivative (B1-1))
To 1000 parts of N-dimethylformamide, 100 parts of 4-nitrophthalonitrile, 79.8 parts of potassium carbonate, N, N-diethyl-1,3-propanediamine 112.8 were added, and the mixture was stirred until 4-nitrophthalonitrile disappeared. .. The disappearance of the raw material was confirmed by UPLC (ultra-high speed high separation liquid chromatography). The reaction solution was added to a mixed solution of 10000 parts of water and 200 parts of chloroform, and the mixture was stirred for 30 minutes. A chloroform layer of this mixed solution was extracted using a separatory funnel. 30 parts of magnesium sulfate was added to the chloroform extract, and the mixture was allowed to stand for 1 hour. Magnesium sulfate was removed and chloroform was distilled off to obtain 119.9 parts (yield 81%) of an intermediate represented by the following chemical formula (3).
After adding 119.9 parts of the intermediate to 840 parts of formamide and stirring, 73 parts of sodium hydroxide was added and the mixture was stirred at 50 ° C. for 2 hours. To the reaction solution, 1200 parts of water and 49.2 parts of 2-cyano-N-methylacetamide were added, and the mixture was stirred at 50 ° C. until the intermediate disappeared. The disappearance of the raw material was confirmed by UPLC. Then, 2400 parts of 80% acetic acid and 68.9 parts of barbituric acid were added, and the mixture was stirred at 85 ° C. for 3 hours. After cooling to room temperature, 28% aqueous ammonia was added so that the pH became 7.0 to 8.0, the non-volatile content was filtered off, and then washed with 1,000 parts of methanol and 2,000 parts of water. The mixture was dried under reduced pressure at 40 ° C. to obtain 115.4 parts (yield 53%) of a pigment derivative (B1-1) (isomer mixture) represented by the following chemical formula (4).

(Pigment derivative (B1-2))
To 1000 parts of N-dimethylformamide, 100 parts of 3-nitrophthalonitrile, 79.8 parts of potassium carbonate, and 125 parts of N, N-diethyl-1,4-butanediamine were added, and the mixture was stirred until 3-nitrophthalonitrile disappeared. The disappearance of the raw material was confirmed by UPLC. The reaction solution was added to a mixed solution of 10,000 parts of water and 200 parts of chloroform, and the mixture was stirred for 30 minutes. A chloroform layer of this mixed solution was extracted using a separatory funnel. 30 parts of magnesium sulfate was added to the chloroform extract, and the mixture was allowed to stand for 1 hour. Magnesium sulfate was removed and chloroform was distilled off to obtain 129.6 parts (yield 83%) of an intermediate represented by the following chemical formula (5).
After adding 129.6 parts of the intermediate to 907 parts of formamide and stirring, 74.8 parts of sodium hydroxide was added and the mixture was stirred at 50 ° C. for 2 hours. To the reaction solution, 1300 parts of water and 49.9 parts of 2-cyano-N-methylacetamide were added, and the mixture was stirred at 50 ° C. until the intermediate disappeared. The disappearance of the raw material was confirmed by UPLC. Then, 2500 parts of 80% acetic acid and 70.6 parts of barbituric acid were added, and the mixture was stirred at 85 ° C. for 3 hours. After cooling to room temperature, 28% aqueous ammonia was added so that the pH became 7.0 to 8.0, the non-volatile content was filtered off, and then washed with 1,000 parts of methanol and 2,000 parts of water. The mixture was dried under reduced pressure at 40 ° C. to obtain 89.7 parts (yield 39%) of a pigment derivative (B1-2) (isomer mixture) represented by the following chemical formula (6).

(Pigment derivative (B1-3))
To 1000 parts of N-dimethylformamide, 100 parts of 4-nitrophthalonitrile, 79.8 parts of potassium carbonate, and 89.4 parts of 3- (dimethylamino) -1-propanol were added, and the mixture was stirred until 4-nitrophthalonitrile disappeared. The disappearance of the raw material was confirmed by UPLC. The reaction solution was added to a mixed solution of 10,000 parts of water and 200 parts of chloroform, and the mixture was stirred for 30 minutes. A chloroform layer of this mixed solution was extracted using a separatory funnel. 30 parts of magnesium sulfate was added to the chloroform extract, and the mixture was allowed to stand for 1 hour. Magnesium sulfate was removed and chloroform was distilled off to obtain 102 parts (yield 77%) of an intermediate represented by the following chemical formula (5).
After 102 parts of the intermediate was added to 713 parts of formamide and stirred, 69.4 parts of sodium hydroxide was added and stirred at 50 ° C. for 2 hours. To the reaction solution, 1000 parts of water and 36.7 parts of 2-cyano-N-methylacetamide were added, and the mixture was stirred at 50 ° C. until the intermediate disappeared. The disappearance of the raw material was confirmed by UPLC. Then, 2000 parts of 80% acetic acid and 65.5 parts of barbituric acid were added, and the mixture was stirred at 85 ° C. for 3 hours. After cooling to room temperature, 28% aqueous ammonia was added so that the pH became 7.0 to 8.0, the non-volatile content was filtered off, and then washed with 1,000 parts of methanol and 2,000 parts of water. The mixture was dried under reduced pressure at 40 ° C. to obtain 107.2 parts (yield 55%) of a pigment derivative (B1-3) (isomer mixture) represented by the following chemical formula (8).

(Pigment derivative (B1-4))
Add 100 parts of 4-nitrophthalonitrile, 79.8 parts of potassium carbonate, and 149.3 parts of N, N-dibutyl-1,2-ethyldiamine to 1000 parts of N-dimethylformamide and stir until 4-nitrophthalonitrile disappears. did. The disappearance of the raw material was confirmed by UPLC. The reaction solution was added to a mixed solution of 10000 parts of water and 200 parts of chloroform, and the mixture was stirred for 30 minutes. A chloroform layer of this mixed solution was extracted using a separatory funnel. 30 parts of magnesium sulfate was added to the chloroform extract, and the mixture was allowed to stand for 1 hour. Magnesium sulfate was removed and chloroform was distilled off to obtain 139.6 parts (yield 81%) of an intermediate represented by the following chemical formula (9).
After adding 139.6 parts of the intermediate to 977 parts of formamide and stirring, 73 parts of sodium hydroxide was added and the mixture was stirred at 50 ° C. for 2 hours. To the reaction solution, 1500 parts of water, 3000 parts of 80% acetic acid and 149.8 parts of barbituric acid were added, and the mixture was stirred at 85 ° C. for 3 hours. After cooling to room temperature, 28% aqueous ammonia was added so that the pH became 7.0 to 8.0, the non-volatile content was filtered off, and then washed with 1,000 parts of methanol and 2,000 parts of water. Drying under reduced pressure at 40 ° C. gave 120.72 parts (yield 48%) of the pigment derivative (B1-4) represented by the following chemical formula (10).

(Pigment derivative (B1-5))
To 1000 parts of N-dimethylformamide, 100 parts of 3-nitrophthalonitrile, 79.8 parts of potassium carbonate, and 101.5 parts of 4- (dimethylamino) -1-butanol were added, and the mixture was stirred until 3-nitrophthalonitrile disappeared. .. The disappearance of the raw material was confirmed by UPLC. The reaction solution was added to a mixed solution of 10,000 parts of water and 200 parts of chloroform, and the mixture was stirred for 30 minutes. A chloroform layer of this mixed solution was extracted using a separatory funnel. 30 parts of magnesium sulfate was added to the chloroform extract, and the mixture was allowed to stand for 1 hour. Magnesium sulfate was removed and chloroform was distilled off to obtain 119.4 parts (yield 85%) of the intermediate represented by the following chemical formula (11).
After adding 119.4 parts of the intermediate to 836 parts of formamide and stirring, 76,6 parts of sodium hydroxide was added, and the mixture was stirred at 50 ° C. for 2 hours. To the reaction solution, 1200 parts of water, 2500 parts of 80% acetic acid and 157.2 parts of barbituric acid were added, and the mixture was stirred at 85 ° C. for 3 hours. After cooling to room temperature, 28% aqueous ammonia was added so that the pH became 7.0 to 8.0, the non-volatile content was filtered off, and then washed with 1,000 parts of methanol and 2,000 parts of water. Drying under reduced pressure at 40 ° C. gave 123.2 parts (yield 52%) of the pigment derivative (B1-5) represented by the following chemical formula (12).

<Production example of the pigment derivative (B2) represented by the general formula (4)>
(Pigment derivative (B2-1))
According to the examples of JP-A-2007-156395, a pigment derivative (B2-1) represented by the following chemical formula (6) was obtained.
Chemical formula (13)

(Pigment derivative (B2-2)
A pigment derivative (B2-2) represented by the following chemical formula (14) was obtained by the same method as in the examples of JP-A-2007-156395 except that diethylaminopropylamine was changed to diethylaminoethylamine. The structure is shown below.
Chemical formula (14)

<Production example of pigment derivative (B3)>
(Pigment derivative (B3-1))
According to Production Example 1 of JP-A-2006-146078, a pigment derivative (B3-1) represented by the following chemical formula (15) was obtained. The structure is shown below.
Chemical formula (15)

<Production example of isoindoline pigment (A1)>
(Miniaturized yellow pigment (A1-1))
C. I. Add 200 parts of Pigment Yellow 139 (BASF Japan's "Palitol Yellow D1819"), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and knead at 80 ° C for 6 hours. did. 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. , A finely divided yellow pigment (A2-1) was obtained.

(Miniaturized yellow pigment (A1-2))
C. I. Add 200 parts of Pigment Yellow 185 (BASF Japan's "Palitol Yellow D1155"), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and knead at 80 ° C for 6 hours. did. 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. , A finely divided yellow pigment (A2-2) was obtained.

(Miniaturized yellow pigment (A1-3))
C. I. Pigment Yellow 185 (BASF Japan's "Palitol Yellow D1155") 140 parts, pigment derivative (B1-1) 60 parts, sodium chloride 1,400 parts, and diethylene glycol 360 parts made of stainless steel 1 gallon kneader (Inoue Seisakusho Co., Ltd.) The product was charged 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. , A finely divided yellow pigment (A1-3) was obtained.

(Miniaturized yellow pigment (A1-4))
C. I. Pigment Yellow 185 (BASF Japan's "Palitol Yellow D1155") 140 parts, pigment derivative (B1-1) 60 parts, carboxylic acid dispersion resin (C2-1) 20 parts, sodium chloride 1,400 parts, And 340 parts of diethylene glycol was 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. , A finely divided yellow pigment (A2-4) was obtained.

<Production examples of pigments other than (A1) and (A2)>
(Miniaturized blue pigment (A3-1))
C. I. Add 200 parts of Pigment Blue 15: 3 (Toyo Color's "Rionol Blue FG7351"), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Kneaded 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. , A finely divided blue pigment (A3-1) was obtained.

<Production example of phosphoric acid-based dispersed resin (C1)>
(Phosphoric acid-based dispersion resin (C1-1) solution)
186 g of lauryl alcohol, 571 g of ε-caprolactone monomer, and 0.6 g of tetrabutyl titanate were charged in a reaction vessel equipped with a nitrogen gas introduction tube, a condenser, and a stirrer, replaced with nitrogen gas, and then heated and stirred at 120 ° C. for 3 hours. .. The disappearance of the caprolactone monomer was confirmed by a GPC (gel permeation chromatography) RI detector using tetrahydrofuran as an eluent. After cooling to 40 ° C. or lower, the mixture is mixed with 84.5 g of polyphosphoric acid having an orthophosphoric acid equivalent content of 116%, gradually heated, and heated at 80 ° C. for 6 hours with stirring to obtain a number average molecular weight of R1 of 760. A phosphoric acid-based resin-type dispersant (C1-1) having an abundance ratio of n = 1 and 2 of 100: 12 was obtained. By adjusting the non-volatile content with propylene glycol monomethyl ether acetate (hereinafter, PGMAc), a phosphoric acid-based dispersed resin (C1-1) solution having a non-volatile content of 30% and an acid value of 166 mgKOH / g per non-volatile content was obtained.

(Phosphoric acid-based dispersion resin (C1-2) solution)
A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer were attached to a separable 4-neck flask, and 1,500 parts of cyclohexanone was charged. , 210 parts of n-butyl methacrylate, 90 parts of 2-hydroxyethyl methacrylate, 60 parts of methacrylic acid, 120 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M-110” manufactured by Toa Synthetic Co., Ltd.), 6 parts of acid phosphoxyethyl methacrylate. A mixed solution of 30 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a phosphoric acid-based dispersed resin (C1-2) solution having a non-volatile content of 30% and a weight average molecular weight of 24,000.

<Production example of carboxylic acid-based dispersed resin (C2)>
(Carboxylic acid-based dispersion resin (C2-1) solution)
In a reaction vessel equipped with a gas introduction tube, temperature, condenser, and stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, i-
70 parts of butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2'-azobisisobutyronitrile was added to 90 parts of PGMAc. It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene were added as a catalyst, and the mixture was reacted at 100 ° C. for 7 hours. .. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and PGMAc was added and diluted so that the non-volatile content was 30% by measuring the non-volatile content, and the acid value was 70 mgKOH / g. , A carboxylic acid-based dispersed resin (C2-1) solution having a weight average molecular weight of 8,500 was obtained.

(Carboxylic acid-based dispersion resin (C2-2) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst are charged, and nitrogen gas is charged. After replacement with, the mixture was heated at 120 ° C. for 4 hours and stirred. After confirming that 98% had reacted by measuring the non-volatile content, 73.3 parts of pyromellitic anhydride was added, and the reaction was carried out at 120 ° C. for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The mixture was adjusted with PGMAc to obtain a carboxylic acid-based dispersed resin (C2-2) solution having a non-volatile content of 30%. The acid value of the obtained carboxylic acid-based dispersed resin (C2-2) was 49 mgKOH / g.

(Carboxylic acid-based dispersion resin (C2-1-1) solution)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 part of dimethylbenzylamine were added. I prepared it. After replacement with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted at 120 ° C. for 4 hours, and then reacted at 80 ° C. for 2 hours. Further, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA (methyl methacrylate (3-ethyloxetane-3-yl), manufactured by Ube Kosan Co., Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc are charged, and a reaction vessel is charged. While keeping the inside at 80 ° C., 0.2 part of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. The non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomers reacted. PGMAc is added and diluted so that the non-volatile content is 30% in the non-volatile content measurement, and the carboxylic acid-based dispersion resin (C2-1-1) having an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000. A solution was obtained.

(Carboxylic acid-based dispersion resin (C2-1-2) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic acid anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged with nitrogen gas. After the substitution, the reaction was carried out at 120 ° C. for 5 hours (first step). By measuring the acid value, it was confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, and 200 parts of methyl acrylate in terms of non-volatile content. 50 parts of methacrylic acid and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80 ° C., 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours. (Second step). It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and 2270 cm based on the isocyanate group by IR. The reaction was carried out until the disappearance of the peak of ^-1 was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and adjusted with PGMAc to obtain a carboxylic acid-based dispersion resin (C2-1-2) solution having a non-volatile content of 30%. The obtained carboxylic acid-based dispersed resin (C2-1-2) had an acid value of 68 mgKOH / g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

<Production example of basic dispersion resin (C3)>
(Basic dispersion resin (C3-1) solution)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst, and at 50 ° C. while flowing nitrogen. The mixture was stirred for 1 hour and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate was charged as an initiator, 5.6 parts of cuprous chloride and 133 parts of PGMAc were charged as a catalyst, and the temperature was raised to 110 ° C. under a nitrogen stream in the first block (B block). Polymerization was started. After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate and 10 parts of methacryloyloxyethyl benzyldimethylammonium chloride as the second block (A block) monomer were added to this reactor, and the temperature was maintained at 110 ° C. under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after charging, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of the non-volatile content, and the reaction solution was brought to room temperature. It was cooled to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20,000, the molecular weight distribution Mw / Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic dispersion resin (C3-1) having a non-volatile content of 169.8 mgKOH / g was obtained. After cooling to room temperature, about 2 g is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc is added so that the non-volatile content becomes 30% by mass, and the basic dispersion resin (C3-1) is added. ) The solution was prepared.

<Manufacturing example of binder resin (D)>
(Binder resin (D-1) solution)
196 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) , 2,2'-Azobisisobutyronitrile 1.1 parts mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20%. A binder resin (D-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

(Binder resin (D-2) solution)
207 parts of cyclohexanone was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethyleneoxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis. A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a resin solution. Next, for the entire amount of the obtained resin solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Showa Denko's Karenz MOI). A mixture of 6.5 parts, 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content becomes 20%. A binder resin (D-2) solution was prepared. The weight average molecular weight (Mw) was 18,000.

(Binder resin (D-3) solution)
370 parts of cyclohexanone 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, the temperature was raised to 80 ° C. 18 parts of Milphenol Ethylene Oxide Modified Acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-azobisisobutyronitrile 2.0. The mixture of parts was added dropwise over 2 hours. After the dropping, the reaction was further carried out at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the non-volatile acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGM Ac was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. A binder resin (D-3) solution was prepared. The weight average molecular weight (Mw) was 19,000.

(Binder resin (D-4) solution)
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Fats), and 40 parts of PGMAc, and use an n-dodecane as a chain transfer agent dropping tank. A well-stirred mixture of 8 parts of thiol and 32 parts of PGMAc was prepared.
After charging 395 parts of PGMAc in the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. in the reaction vessel. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were charged in the reaction vessel, and the mixture was allowed to react at 110 ° C. for 12 hours. rice field. After that, 150 parts of PGMAc is added and cooled to room temperature, about 2 g of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized resin solution. As described above, PGMAc was added to obtain a binder resin (D-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile component was 2 mgKOH / g.

<Manufacturing of coloring composition>
[Example 1]
(Coloring composition (PB-1))
The following raw materials are stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The colored composition (PB-1) was prepared by filtering with a 0 μm filter. The organic solvent (P-1) is PGMAc.
Finely divided phthalocyanine green pigment (A2-2): 9.36 parts by mass Finely divided yellow pigment (A1-2): 2.34 parts by mass Pigment derivative (B1-1): 1.30 parts by mass Dispersed resin (C2) -1) Solution: 15.91 parts by mass Binder resin (D-1) solution: 4.00 parts by mass Organic solvent (P-1): 67.09 parts by mass

[Examples 2-31, Comparative Examples 1-9]
(Coloring Compositions (PB-2-31, PB-34-42))
Coloring compositions (PB-2-31, PB-34-42) were prepared in the same manner as in Example 1 except that the material types and masses were changed as shown in Table 1.
Got

[Example 32]
(Coloring Composition (PB-32))
The following components are stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. A colored composition (GB-32) was prepared by filtering with a 0 μm filter.
Finely divided phthalocyanine green pigment (A2-2): 12.50 parts by mass Pigment derivative (B2-2): 0.50 parts by mass Dispersion resin (C3-1) solution: 14.44 parts by mass Binder resin (D-1) ) Solution: 13.34 parts by mass Organic solvent (P-1): 59.22 parts by mass

The following components are stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. A colored composition (YB-32) was prepared by filtering with a 0 μm filter.
Finely divided yellow pigment (A1-3): 13.00 parts by mass Distributed resin (C2-1) solution: 21.67 parts by mass Binder resin (D-1) solution: 2.50 parts by mass Organic solvent (P-1) ): 62.83 parts by mass

The following components were stirred and mixed so as to be uniform, and filtered through a filter having a pore size of 1.0 μm to prepare a colored composition (PB-32).
Coloring composition (GB-32): 75 parts by mass Coloring composition (YB-32): 25 parts by mass

[Example 33]
(Coloring Composition (PB-33))
The following components are uniformly stirred and mixed, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then a filter having a pore diameter of 1.0 μm. The mixture was filtered with (YB-33) to prepare a colored composition (YB-33).
Finely divided yellow pigment (A1-4): 13.0 parts by mass Distributed resin (C2-1) solution: 20.37 parts by mass Binder resin (D-1) solution: 4.45 parts by mass Organic solvent (P-1) ): 62.18 parts by mass

The following components were stirred and mixed so as to be uniform, and filtered through a filter having a pore size of 1.0 μm to prepare a colored composition (PB-33).
Coloring composition (GB-32): 75 parts by mass Coloring composition (YB-33): 25 parts by mass

<Evaluation of coloring composition>
The obtained colored compositions (PB-1 to 42) were evaluated for initial viscosity, dispersion stability, and foreign matter by the following methods. The evaluation results are shown in Table 2.

(Initial viscosity evaluation)
The measurement was performed using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.) under the condition of a rotation speed of 50 rpm at 25 ° C. 3 or more can be used without any problem in practical use.
5:10 mPa · S or less 4: 10 mPa · S or more, 15 mPa · S or less 3: 15 mPa · S or more, 30 mPa · S or less 2:30 mPa · S or more, 50 mPa · S less than 1: 50 mPa · S or more

(Dispersion stability evaluation)
The initial viscosity of the day after the coloring composition was prepared and the viscosity over time accelerated at 40 ° C. for 1 week were measured at 25 ° C. using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). The measurement was performed under the condition that the rotation speed was 50 rpm. From the initial viscosity and the value of the viscosity with time, the rate of change in viscosity with time was calculated by the following formula, and the dispersion stability was evaluated. 3 or more can be used without any problem in practical use.
Formula: [Ratio of change in viscosity over time] = | ([Initial viscosity]-[Viscosity over time]) / [Initial viscosity] | × 100
5: Change rate less than 5% 4: Change rate 5% or more and less than 10% 3: Change rate 10% or more, less than 15% 2: Change rate 15% or more, less than 20% 1: Change rate 20% or more

(Foreign matter evaluation)
A coloring composition was applied onto the transparent substrate so that the dry coating film had a size of about 2.0 μm, and heat treatment was performed at 230 ° C. for 1 hour in an oven to measure the number of foreign substances in the coating film. For the evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus System Corporation). The magnification was set to 500 times, and the number of foreign substances observable in any five fields of view was measured by transmission. 3 or more is not a problem in practice.
5: The number of foreign substances is less than 5 4: The number of foreign substances is 5 or more and less than 10
3: The number of foreign substances is 10 or more and less than 20
2: The number of foreign substances is 20 or more and less than 100
1: The number of foreign substances is 100 or more

<Preparation of photosensitive coloring composition>
[Example 101]
(Photosensitive coloring composition (PR-1))
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (PR-1).
Coloring composition (PB-1): 74.0 parts by mass
Binder resin (D) solution: 2.0 parts by mass Epoxy compound (G-1): 0.2 parts by mass Oxetane compound (G-2): 0.2 parts by mass Photopolymerizable compound (E): 2.0 parts by mass Part Photopolymerization initiator (F): 1.0 part by mass Sensitizer (H): 0.1 part by mass Thiol-based chain transfer agent (I): 0.3 part by mass Polymerization inhibitor (J): 0.1 Parts by mass Ultraviolet absorber (K): 0.1 parts by mass Antioxidant (L): 0.1 parts by mass Leveling agent (M): 1.0 parts by mass Storage stabilizer (N): 0.1 parts by mass Silane Coupling agent (O): 0.2 parts by mass Organic solvent (P): 18.6 parts by mass

[Examples 102 to 133, Comparative Examples 101 to 109]
(Photosensitive coloring compositions PR-2 to PR-42)
Photosensitive coloring compositions (PR-2-42) were prepared in the same manner as in Example 101, except that the type of the coloring composition PB-1 of Example 101 was changed to that shown in Table 2.
The raw materials are as follows.

(Binder resin (D) solution)
The binder resins (D-2) to (D-4) were mixed in the same amount to prepare a binder resin (D) solution.

(Epoxy compound (G-1))
(G-1-1) 2,2'-bis (hydroxymethyl) -1-butanol 1,2-
Epoxy-4- (2-oxylanyl) cyclohexane adduct
[EHPE-3150 (manufactured by Daicel)],
(G-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase Chemtex)],
(G-1-3) Triglycidyl isocyanurate The same amounts of the above (G-1-1) to (G-1-3) were mixed to obtain an epoxy compound (G-1).

(Oxetane compound (G-2))
3-Ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane
[Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

(Polymerizable compound (E))
(E-1) Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(E-2) Trimethylolpropane EO-modified triacrylate
[Aronix M350 (manufactured by Toagosei)]
(E-3) Dipentaerythritol penta and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(E-4) Polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(E-5) Caprolactone-modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]
As described above, (E-1) to (E-5) were mixed in the same amount to obtain the polymerizable compound (E).

(Photopolymerization Initiator (F))
(F-1) 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(F-2) Ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(F-3) Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
[Irgacure 819 (manufactured by BASF Japan)]
(F-4) Irgacure OXE04 (manufactured by BASF Japan)
(F-5) ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation)
(F-6) TR-PBG-345 (manufactured by Changzhou Strong New Materials Co., Ltd.)

以上、（Ｆ－１）～（Ｆ－１０）をそれぞれ同量にて混合し、光重合開始剤（Ｆ）とした。

As described above, (F-1) to (F-10) were mixed in the same amount to obtain a photopolymerization initiator (F).

(Sensitizer (H))
(H-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4'-bis (diethylamino) benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (H-1) and (H-2) were mixed in the same amount to obtain a sensitizer (H).

(Thiol chain transfer agent (I))
(I-1) Trimethylolethane ethanetris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(I-2) Trimethylolpropane Tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(I-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-4) Trimethylolpropane Tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(I-5) Tris [(3-mercaptopropionyloxy) -ethyl] -isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
As described above, (I-1) to (I-5) were mixed in the same amount to prepare a thiol-based chain transfer agent (I).

(Polymerization inhibitor (J))
(J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) t-Butylhydroquinone or more, (J-1) to (J-3) are mixed in the same amount, and a polymerization inhibitor is added. It was designated as (J).

(Ultraviolet absorber (K))
(K-1) 2- [4-[(2-Hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 ， 3,5-Triazine
[TINUVIN400 (manufactured by BASF Japan)]
(K-2) 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
[TINUVIN900 (manufactured by BASF Japan)]
As described above, (K-1) to (K-2) were mixed in the same amount to obtain an ultraviolet absorber (K).

(Antioxidant (L))
(L-1) Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (L-2) 3,3'-dioctadecylthiodipropanoate (L-3) tris [2] , 4-Di- (t) -Butylphenyl] Phenyl (L-4) Bis (2,2,6,6-Tetramethyl-4-piperidyl) Sevacate (L-5) Salicylic acid p-octylphenyl or higher, (L) -1) to (L-5) were mixed in the same amount to prepare an antioxidant (L).

(Leveling agent (M))
(M-1) "BYK-330" manufactured by Big Chemie
(M-2) "Mega Fuck F-551" manufactured by DIC Corporation
(M-3) "Emargen 103" manufactured by Kao Corporation
As described above, 1 part each of (M-1) to (M-3) was mixed, and the mixed solution dissolved in 97 parts of PGMAc was used as the leveling agent (M).

(Storage stabilizer (N))
(N-1) 2,6-bis (1,1-dimethylethyl) -4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(N-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (N-1) to (N-2) were mixed in the same amount to prepare a storage stabilizer (N).

(Adhesion improver (O))
(O-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-3) N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(O-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
As described above, (O-1) to (O-4) were mixed in the same amount to prepare a silane coupling agent (O).

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring composition was evaluated for spectral characteristics (film thickness), alkali developability, and pattern forming property by the following methods. The evaluation results are shown in Table 3.

(Evaluation of spectral characteristics (film thickness))
A resist solution for a flattening film ("HL-18s" manufactured by Nippon Steel Chemical Co., Ltd. "is applied by a spin coating method on a glass substrate having a thickness of 100 mm x 100 mm and 1.1 mm, heated on a hot plate at 100 ° C. for 6 minutes, and then 230. The coating film was cured by heating in an oven at ° C. for 1 hour to obtain a glass substrate with a flat film.
Next, the photosensitive coloring composition of Comparative Example 101 was applied onto the flattening film by adjusting the rotation speed of the spin coater so that the film thickness after post-baking was 0.50 μm. After coating, prebaking was performed on a hot plate at 70 ° C. for 1 minute, and then ultraviolet exposure was performed using an ultrahigh pressure mercury lamp with an illuminance of 30 mW / cm ² and an exposure amount of 500 mJ / cm ² . The coated film after exposure was paddle-developed with an organic alkaline developer for 1 minute. After paddle development, it was washed with pure water in a spin shower for 20 seconds, the remaining water droplets were blown off with high-pressure air, and the coated substrate was post-baked at 230 ° C. for 20 minutes and then allowed to cool.
The chromaticity of the obtained coating film of Comparative Example 101 was measured with a microspectrophotometer (“OSP-SP100” C light source manufactured by Olympus Optical Co., Ltd.).
Next, the photosensitive coloring compositions of Examples 101 to 128 and Comparative Examples 102 to 104 were coated with different film thicknesses so as to have the same chromaticity as Comparative Example 101, and coated by the same operation as Comparative Example 101. Got
The film thickness of Comparative Example 101 was set to 100, and the film thickness of each photosensitive coloring composition was evaluated as a relative value. Two or more can be used without problems in practical use.
The film thickness of the obtained coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).
5: 70 or more 4: 70 or more and less than 80 3: 80 or more and less than 90 2: 90 or more and less than 100 1: 100 or more

By the above method for evaluating the spectral characteristics (film thickness), the film thickness of each photosensitive coloring composition of Comparative Examples 105 to 109 is set to 100, and the relative value of each photosensitive coloring composition of Examples 129 to 133 is set to 100. The spectral characteristics (film thickness) were evaluated.

(Evaluation of alkali developability)
A resist solution for a flattening film ("HL-18s" manufactured by Nippon Steel Chemical Co., Ltd. "is applied by a spin coating method on a 6-inch silicon wafer, heated on a hot plate at 100 ° C for 6 minutes, and then placed in an oven at 230 ° C. The coating film was cured by heating for a time to obtain a silicon wafer with a flat film. Next, the photosensitive coloring composition was spin-coated on the flattening film so that the film thickness after drying was 0.5 μm. To form 1.0 μm square pixels at a wavelength of 365 nm using the i-line stepper exposure device FPA-3000i5 + (manufactured by Canon), coated by method, prebaked on a hot plate at 100 ° C. for 1 minute. A pattern exposure was performed with an exposure amount of 150 mJ / cm ² through a photo mask. The coated film after exposure was paddle-developed with an organic alkaline developer. After paddle-development, it was washed with pure water in a spin shower for 20 seconds. , The water droplets remaining on the wafer are blown off with high-pressure air, the substrate is naturally dried, a square pixel pattern is formed, and the surface of the unexposed part washed away by development is surfaced with a scanning electron microscope (Hitachi High-Tech Co., Ltd. "S-". The alkali developability was determined by the presence or absence of a residue by observing with 3000 N "). 3 or more can be used without any problem in practical use.
5: No residue in 1 minute of development time 4: Slight residue is seen in 1 minute of development time 3: Slight residue is seen in 1 minute of development time 2: Residue is seen in 1 minute of development time 1: Development time 1 Severe residue is seen in minutes

(Pattern formation)
A test substrate was formed by the same procedure as the above-mentioned alkaline developability test, and the pattern size of 1.0 μm square in the pattern in the development was observed with a scanning electron microscope (“S-3000N” manufactured by Hitachi High-Tech Corporation). 3 or more can be used without any problem in practical use.
5: Pattern size is 0.9 μm or more and less than 1.2 μm 3: Pattern size is 0.7 μm or more and less than 0.9 μm, or 1.2 μm or more and less than 1.4 μm 1: Pattern size is less than 0.7 μm, 1.4 μm or more

Claims (10)

A coloring composition containing an organic pigment (A), a pigment derivative (B), and a dispersed resin (C), wherein the pigment derivative (B) is a pigment derivative (B1) represented by the general formula (1). Including
A coloring composition comprising the dispersion resin (C) at least one of a phosphoric acid-based dispersion resin (C1) and a carboxylic acid-based dispersion resin (C2).

[In the general formula (1), one of R ₁ to R ₄ has a substituent represented by the general formula (2), and the other represents a hydrogen atom.
X represents —O— or —NH—, Y represents a divalent linking group containing an unsubstituted alkylene group, and _R5 to _R6 represent an unsubstituted alkyl group. ] The coloring composition according to claim 1, wherein the organic pigment (A) contains an isoindoline pigment (A1) and a phthalocyanine green pigment (A2). The content of the phosphoric acid-based dispersion resin (C1) and the carboxylic acid-based dispersion resin (C2) is 50 to 1000 parts by mass with respect to 100 parts by mass of the pigment derivative (B1) represented by the general formula (1). The coloring composition according to claim 1 or 2, which is a part. The phosphoric acid-based dispersion resin (C1) contains the following dispersion resin (C1-1) or (C1-2), and the carboxylic acid-based dispersion resin (C2) is the following (C2-1) or (C2). The coloring composition according to any one of claims 1 to 3, which comprises the dispersed resin of -2).
(C1-1): Dispersed resin represented by the following general formula (3).
(HO-) _3-n- PO- (OR ¹ ) _n General formula (3)
(In the general formula (3), R ¹ represents a polyester residue having a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)
(C1-2): Dispersed resin containing a phosphoric acid group-containing monomer unit and other monomer units.
(C2-1): A carboxyl product of an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides and a hydroxyl group in a hydroxyl group-containing compound. A dispersion resin containing a polyester moiety having a group and a vinyl polymer moiety.
(C2-2): Dispersed resin represented by the following general formula (4).
(HOOC-) _m -R ^2- (-COO- [-R ⁴ -COO-] _n -R ³ ) _t General formula (4)
(In the general formula (4), R ² is a tetravalent tetracarboxylic acid compound residue, R ³ is a monoalcohol residue, R ⁴ is a lactone residue, m is 2 or 3, and n is an integer of 1 to 50. t represents (4-m).) The coloring composition according to claim 4, wherein the dispersion resin of (C2-1) contains the dispersion resin represented by any of the following (C2-1-1) or (C2-1-2).
(C2-1-1): One or more heat-crosslinkable group-containing monomer units selected from the group in which the vinyl polymer moiety consists of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group, and Dispersed resin containing a carboxyl group-containing monomer unit.
(C2-1-2): A dispersion resin having a polymerizable unsaturated group in the vinyl polymer portion. The coloring composition according to any one of claims 1 to 5, wherein the dispersion resin (C) contains a basic dispersion resin (C3). The coloring composition according to any one of claims 1 to 6, wherein the pigment derivative (B) contains a pigment derivative (B2) represented by the following general formula (5).
General formula (5)

(In the general formula (5), R ¹ to R ⁹ each independently have a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 20 or less carbon atoms which may have a substituent, and a substituent. It represents an alkoxy group having 20 or less carbon atoms or an aryl group having 20 or less carbon atoms which may have a substituent, and adjacent substituents may be bonded to each other to form an aliphatic ring or an aromatic ring. Good. Q represents a divalent linking group. A and B are independently a group represented by the following general formula (6), a group represented by the following general formula (7), and —O—. (CH ₂ ) represents a group selected from _n -R ¹⁰ , -OR ¹¹ , -NR ¹² R ¹³ , -Cl, and -F, where R ¹⁰ represents a optionally substituted nitrogen-containing heterocyclic residue. R ¹¹ , R ¹² , and R ¹³ each have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 to 20 carbon atoms which may have a substituent. It represents an aryl group having 6 to 20 carbon atoms which may have an alkenyl group or a substituent, and n represents an integer of 0 to 20.

(In the general formula (6), Y ¹ represents -NR ^20- or -O-, and Y ² may have a substituent and has an alkylene group having 1 to 20 carbon atoms and a substituent. It represents an alkenylene group having 2 to 20 carbon atoms which may be present, or an arylene group having 6 to 20 carbon atoms which may have a substituent, and these groups are -NR ^20- , -O-,. They may be bonded to each other with a divalent linking group selected from -SO _2- and -CO-. R20 may have a hydrogen atom and a substituent and may have a substituent and an alkyl having 1 to ²⁰ carbon atoms. A group, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ¹⁴ and R ¹⁵ represent. Each represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent. R ¹⁴ and R ¹⁵ are integrated. Therefore, a heterocyclic structure may be formed which may contain and be substituted with an additional nitrogen atom, oxygen atom or sulfur atom.
In the general formula (7), Z ¹ is a single bond connecting a triazine ring and a nitrogen atom, -NR ^21- , -NR ²¹ -G-CO-, NR ²¹ -G-CONR ^22- , -NR ²¹ -G-SO. _2- , -NR ²¹ -G-SO ₂ NR ^22- , -OG-CO-, -OG-CONR ^21- , -OG-SO _2- , or -OG-SO ₂ NR ^{Representing 21-} , G has an alkylene group having 1 to 20 carbon atoms which may have a substituent and an alkenylene group or a substituent having 2 to 20 carbon atoms which may have a substituent. Representing an arylene group having 6 to 20 carbon atoms which may be present, R ²¹ and R ²² have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent, respectively. It represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ each have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 2 carbon atoms which may have a substituent. An alkenyl group of up to 20 or an aryl group having 6 to 20 carbon atoms which may have a substituent and R18 is an alkyl group having 1 to ²⁰ carbon atoms which may have a substituent. Alternatively, it represents an alkenyl group having 2 to 20 carbon atoms which may have a substituent. ) A photosensitive coloring composition comprising the coloring composition according to any one of claims 1 to 7, the polymerizable compound (E), and the photopolymerization initiator (F). A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition of claim 8. A solid-state image sensor comprising the color filter according to claim 9.