JP6160286B2 - Coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for producing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent solvent resistance and heat resistance as a colorant is mainly used.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

  In recent years, in order to realize a high contrast ratio and high brightness that cannot be achieved with a pigment, a technique using a dye as a colorant has been proposed, as in Patent Document 1. However, as described in Patent Document 2, for example, dye characteristics tend to be inferior in fastness such as heat resistance and light resistance as compared with pigments. So far, solutions have been studied as in Patent Documents 3 and 4, but there are disadvantages such as poor solvent resistance necessary for adapting as a color filter and incompatibility as a member. Moreover, as described in Patent Document 5, dyes tend to have poor solubility in organic solvents suitable as colored products for color filters. Therefore, in the use of dyes, there is a demand for a solution to the technical problem of both solvent solubility and fastness.

JP-A-6-75375 JP-A-8-327811 JP2012-098522A JP 2012-173399 A JP 2008-304766 A

  An object of the present invention is to provide a coloring composition for a color filter having high brightness and excellent heat resistance and solvent resistance, and a color filter using the same.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have found that the photocationic polymerization initiator (A) having a specific structure, a triarylmethane basic dye, and an anionic group And a salt-forming compound (B) composed of a counter compound having a high lightness and a performance that is excellent in heat resistance and light resistance. It is.

  That is, the present invention relates to a colorant containing a salt-forming compound (B) of a triarylmethane basic dye and a counter compound having an anionic group, a binder resin, a solvent, and a photocationic polymerization initiator (A). The coloring composition for color filters characterized by containing these.

  Moreover, this invention relates to the coloring composition for color filters characterized by the photocationic polymerization initiator (A) containing aromatic sulfonium salt (A1) or aromatic iodonium salt (A2).

  The present invention also relates to the coloring composition for a color filter, wherein the counter compound of the salt-forming compound (B) is an organic sulfonic acid or a metal salt thereof, or a resin having an anionic group in a side chain. .

The present invention also relates to the coloring composition for a color filter, wherein the organic sulfonic acid or a metal salt thereof is represented by the following general formula (11).
Formula (11)
[In General Formula (11), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, and M + each independently represents a hydrogen ion or a metal ion. n represents an integer of 1 to 4. ]

Moreover, this invention relates to the said coloring composition for color filters characterized by the organic sulfonic acid or its metal salt being the ethylenically unsaturated monomer (a-1) shown to General formula (21).
General formula (1)
[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group.
R ² represents a single bond or a divalent linking group,
A represents the general formula (2), and Y ⁺ represents an inorganic or organic cation. ]
General formula (2)
[In General Formula (2), R ⁴ represents an alkylene group which may have a substituent, and n is an integer of 1 to 20. ]

  In addition, the present invention relates to the colored composition for a color filter, further comprising a photopolymerizable monomer (C) and / or a photopolymerization initiator (D).

  The present invention also relates to the color composition for color filters, further comprising an antioxidant (E).

  The present invention also relates to a color filter comprising a filter segment formed on the substrate from the color filter coloring composition.

  The colored composition for a color filter of the present invention contains a photocationic polymerization initiator (A), and thus has excellent heat resistance and light resistance, and can achieve higher brightness. Therefore, the color filter excellent in the characteristic can be provided by using the coloring composition for color filters of the present invention.

Hereinafter, the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” mentioned in the present specification means a color index (CI).

The coloring composition for a color filter of the present invention includes a colorant containing a salt-forming compound (B) of a triarylmethane basic dye and a counter compound having an anionic group, a binder resin, a solvent, and photocationic polymerization. First, the various components of the coloring composition for a color filter of the present invention will be described.

<Colorant>
The coloring composition for a color filter of the present invention contains a salt-forming compound (B) of a triarylmethane basic dye and a counter compound having an anionic group as a colorant. By including the salt-forming compound (B), the solubility in an organic solvent is good, and the fastness such as heat resistance is also excellent.

<< Salt Formation Compound (B) >>
The salt-forming compound (B) is a salt-forming compound comprising a triarylmethane-based basic dye and a counter compound having an anionic group, and a color filter coloring composition using such a salt-forming compound (B) By using the color filter, it is possible to obtain a color filter having good heat resistance and light resistance and having higher brightness.

  Such a triarylmethane-based basic dye and a counter compound react by dissolving both in an aqueous solution, an alcohol solution, or the like to obtain a salt-forming compound (B). Or it is also possible to obtain by melt-kneading both, heating.

[Triarylmethane basic dye]
The triarylmethane basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, the triaminoarylmethane-based basic dye is preferable in terms of good blue, red and green coloring.
a) Diaminotriarylmethane basic dye b) Triaminotriarylmethane basic dye c) Rosolic acid basic dye having an OH group Triaminotriarylmethane basic dye, diaminotriarylmethane basic The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable.

  Since the blue triarylmethane basic dye has a spectral characteristic having a high transmittance at 400 to 440 nm, it can have a high brightness particularly when used for forming a blue filter segment. This is preferable because it is possible.

Specific examples of triarylmethane basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like.
Above all, from the point of brightness, C.I. I. Basic Blue 7 is preferably used.

[Counter compound]
In the present invention, a counter compound as an anion component that can be preferably used is an anionic compound having a molecular weight in the range of 200 to 3,500, or a resin having an anionic group in the side chain. Specific examples of the anionic compound having a molecular weight in the range of 200 to 3500 include heteropolyacids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, and organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids. , An organic acid such as an aromatic carboxylic acid, an organic carboxylic acid such as a fatty acid, or an acid dye. Alternatively, a metal salt thereof may be used.

Further, as described in cationic photopolymerization initiator (A), the counter anion Y ^- is a also good, among them, fluorine-containing phosphate anion, fluorine-containing boron anion, cyano group-containing nitrogen anion, a halogenated hydrocarbon group Those having a conjugated base of an organic acid having a resistance are particularly preferred from the viewpoint of imparting resistance.

When the molecular weight of the counter compound is smaller than 200, the heat resistance and light resistance are lowered, and when the molecular weight of the counter compound is larger than 3500, the ratio of the coloring component per molecule is lowered and sufficient color development is achieved. It becomes impossible.
Furthermore, modification with a resin having an acid group is also preferable.

  Among these, the counter compound as an anion component having a molecular weight in the range of 200 to 3500 is in the form of organic acid such as organic sulfonic acid or organic carboxylic acid, organic sulfuric acid such as aliphatic sulfuric acid, aromatic sulfuric acid, or acidic dye. It is preferable to have. Among these, the form of organic sulfonic acid, aliphatic sulfuric acid or aromatic sulfuric acid or acidic dye is preferable, and organic sulfonic acid, aliphatic sulfuric acid or aromatic sulfuric acid is more preferable.

  The molecular weight and average molecular weight defined in the present invention are expressed by theoretical values converted from atomic weights. The first decimal place was calculated as a significant figure, and the calculated value was rounded off to exclude the minority. When the counter compound is used as a metal salt such as a sodium salt, the molecular weight is considered after replacing Na with H, for example.

(Heteropoly acid)
The heteropoly acid, phosphotungstic acid _{H 3 (PW 12 0 40)} · nH 2 O (n ≒ 30:. ≒ is representative of the the nearly equal) (molecular weight 3421), silicotungstic acid _{H 4 (SiW 12 0 40)} · _{nH 2 O (n ≒ 30)} ( molecular weight 3418), phosphomolybdic acid _{H 3 (PMo 12 0 40)} · nH 2 O (n ≒ 30) ( molecular weight 2205), silicomolybdic acid _{H 3 (SiMo 12 0 40)} · nH ₂ O (n≈30) (molecular weight 2202), phosphotungstomolybdic acid H ₃ (PW _{12 -X} Mo _X 0 ₄₀ ) · nH ₂ O (n≈30) (6 <X <12), phosphovanadomolybdic acid _{H 15-X (PV 12 -} X Mo X 0 40) · nH 2 O (n ≒ 30) , and the like.
In addition, the molecular weight of phosphotungstomolybdic acid, phosphovanadomolybdic acid, and cytungstomolybdic acid is adjusted within the range of 2202 to 3421 by changing the composition ratio of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, and the like. be able to.
Moreover, when using a heteropolyacid as a counter compound, it is preferable that the average molecular weights are the range of 2820-3421. This is because when molybdenum and tungsten are included, the proportion of tungsten is preferably more than 50%. In the case of phosphotungstomolybdic acid, a colorant having excellent transparency can be obtained by reducing the Mo content and including a large amount of W.

(Organic acid)
Examples of organic acids include organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, and their metals. Salt. Further, it may be a salt such as an ammonium salt.
Among these organic acids, organic sulfonic acids such as aliphatic sulfonic acid and aromatic sulfonic acid, and organic sulfuric acid such as aliphatic sulfuric acid and aromatic sulfuric acid are preferable from the viewpoint of hue, heat resistance and solvent resistance. Of these, aliphatic sulfuric acid or aromatic sulfuric acid represented by the following general formula (11) or general formula (12), that is, an aliphatic sulfuric acid ester or an aromatic sulfuric acid ester is preferable because of excellent color reproducibility. Moreover, the monomer which has a sulfonic acid group represented with the ethylenically unsaturated monomer (a-1) shown to the below-mentioned general formula (21) can also be used suitably at the point of heat resistance and solvent resistance. . An organic sulfonic acid or a metal salt thereof is also preferable because it is particularly excellent in color reproducibility.

  In the case of an organic acid, the preferred counter compound has a molecular weight range of 200 to 750, and a more preferred molecular weight range of 200 to 400. Even more preferably, it is in the range of 250-400. By setting the molecular weight within this range, it is possible to obtain a colorant having a good balance between resistance and coloring power, which is preferable.

[Aliphatic sulfuric acid represented by general formula (11) or general formula (12)]
Formula (11)
[In General Formula (11), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, and M + each independently represents a hydrogen ion or a metal ion. n represents an integer of 1 to 4. ]

Specific examples of M include a hydrogen atom, an alkali metal, and an alkaline earth metal. Examples of the alkali metal include sodium, potassium, and lithium, and examples of the alkaline earth metal include calcium and magnesium.
When n is 2 or more, M may be the same or different.

Formula (12)
[In General Formula (12), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, and M ′ ^{m +} each independently represents a metal ion. m represents an integer of 2 to 4. ]

  Specific examples of M ′ include alkaline earth metals and transition metals. Examples of the alkaline earth metal include calcium and magnesium, and examples of the transition metal include manganese and copper.

  Examples of the substituted or unsubstituted alkyl group in R include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms, or one or more ester bonds having 2 to 30 carbon atoms ( -COO-) and / or a linear, branched, monocyclic or condensed polycyclic alkyl group containing an ether bond (-O-).

  Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, 2-ethylhexyl group, tert- An octyl group, a 4-decylcyclohexyl group, and the like can be mentioned, but are not limited thereto.

Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and containing one or more ester bonds include —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₃ , —CH _{2 -CH (-CH 3) -CH 2} -COO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -CH 2 _{-COO-CH 2 -CH (CH 2} -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, - (CH 2) 5 -COO- (CH 2) 11 -CH 3, -CH 2 -CH _{2 -CH 2 -CH- (COO-CH} 2 -CH 3) can be exemplified _2, etc., but is not limited thereto.

Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and including one or more ether bonds include — (CH ₂ —CH ₂ —O) _t —CH ₃ (where t 3 from a 8), - (CH ₂ is _{-CH 2 -CH 2 -O) p-} CH 3 ( where p is 2 to 5), but can be given, are limited to It is not a thing.

Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 30 carbon atoms and optionally including one or more ether bonds include the following, but are not limited thereto. Absent.

Furthermore, specific examples of linear, branched, and alkyl groups having 3 to 30 carbon atoms and including one or more ester bonds (—COO—) and ether bonds (—O—) include —CH ₂ — _{CH 2 -COO-CH 2 -CH 2} -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, -CH 2 -CH 2 -COO-CH 2 -CH _{2 -O-CH 2 -CH 2 -O} -CH 2 -CH (CH 2 -CH 3) can be exemplified _{-CH 2 -CH 2 -CH 2 -CH 3} , but the invention is not limited to .

  Examples of the substituted or unsubstituted alkenyl group for R include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. They may have a plurality of carbon-carbon double bonds in the structure. Specific examples include 1-octenyl group, 2-octenyl group, 3-octenyl group, 4-octenyl group, 5-octenyl group, 6-octenyl group, 7-octenyl group, and the like. It is not limited.

  Preferred compounds as the aromatic sulfonic acid include 1-naphthylamine-4,8-disulfonic acid (molecular weight 303), 1-naphthylamine-3,8-disulfonic acid (molecular weight 303), 1-naphthylamine-5,7-disulfonic acid ( Molecular weight 303), 1-naphthylamine-3,6-disulfonic acid (molecular weight 303), 1-naphthylamine-3,6,8-trisulfonic acid (kofoic acid) (molecular weight 383), 2-naphthylamine-6,8-disulfone Acid (molecular weight 303), 2-naphthylamine-1,6-disulfonic acid (molecular weight 303), 2-naphthylamine-4,8-disulfonic acid (molecular weight 303), 2-naphthylamine-3,6-disulfonic acid (amino-R) Acid) (molecular weight 303), 2-naphthylamine-5,7-disulfonic acid (amino J acid) (molecular weight 303) 1-naphthol-4,8-disulfonic acid (molecular weight 304), 1-naphthol-3,8-disulfonic acid (ε acid) (molecular weight 304), 1-naphthol-3,6-disulfonic acid (molecular weight 304), 1 -Naphthol-3,6,8-trisulfonic acid (molecular weight 384), 2-naphthol-6,8-disulfonic acid (molecular weight 304), 2-naphthol-3,6-disulfonic acid (R acid) (molecular weight 304) 2-naphthol-3,6,8-trisulfonic acid (molecular weight 384), N-phenyl-1-naphthylamine-8-sulfonic acid (molecular weight 299), Np-tolyl-1-naphthylamine-8-sulfonic acid (Molecular weight 313), N-phenyl-1-naphthylamine-5-sulfonic acid (molecular weight 299), N-phenyl-2-naphthylamine-6-sulfonic acid (molecular weight 29) 9), N-acetyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 315), N-acetyl-6 -Amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-6-amino-1-naphthol-3-sulfonic acid (molecular weight 315), 1,8-dihydro-3,6-disulfonic acid ( Chromotropic acid) (molecular weight 320), 8-amino-1-naphthol-3,6-disulfonic acid (molecular weight 319), 8-amino-1-naphthol-5,7-disulfonic acid (molecular weight 319), 1,6 -Diamino-2-naphthol-4-sulfonic acid (molecular weight 254), 1-amino-2-naphthol-6,8-disulfonic acid (molecular weight 319), 1-amino-2-naphtho 3,6-disulfonic acid (molecular weight 319), 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334), 2,7-diamino-1-naphthol-3-sulfonic acid (molecular weight) 254), 2,6-diamino-1-naphthol-3-sulfonic acid (molecular weight 254), 2,8-diamino-1-naphthol-3,6-disulfonic acid (molecular weight 334), 2-amino-7-phenyl Amino-1-naphthol-3-sulfonic acid (molecular weight 330), 7-aminonaphthalene-1,3,6-trisulfonic acid (molecular weight 383), 1-amino-2,3,5-naphthalene trisulfonic acid (molecular weight) 383), 4-amino-1,2,3-naphthalene trisulfonic acid (molecular weight 383), 1-amino-2,3,6-naphthalene trisulfonic acid (molecular weight 383), 4 Amino-2,3,6-naphthalene trisulfonic acid (molecular weight 383), 4-amino-2,3,5-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,3,8-naphthalene trisulfonic acid (Molecular weight 383), 4-amino-1,3,7-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,3,6-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,3 , 5-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,2,8-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,2,7-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,2,6-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,2,5-naphthalene trisulfonic acid (molecular weight 383), 5-amino -1,2,6-naphthalene trisulfonic acid (molecular weight 383), 5-amino-1,3,6-naphthalene trisulfonic acid (molecular weight 383), 5-amino-1,4,6-naphthalene trisulfonic acid ( Molecular weight 383), 5-amino-2,3,6-naphthalene trisulfonic acid (molecular weight 383), 8-amino-1,3,7-naphthalene trisulfonic acid (molecular weight 383), 8-amino-1,2, 7-naphthalene trisulfonic acid (molecular weight 383), 5-amino-1,2,7-naphthalene trisulfonic acid (molecular weight 383), 5-amino-1,3,7-naphthalene trisulfonic acid (molecular weight 383), 8 -Aminonaphthalene-1,4,6-trisulfonic acid (molecular weight 383), 5-amino-2,3,7-naphthalene trisulfonic acid (molecular weight 383), 8-aminonaphth Len-1,3,6-trisulfonic acid (molecular weight 383), 8-amino-1,2,6-naphthalene trisulfonic acid (molecular weight 383), 5-amino-1,2,8-naphthalene trisulfonic acid ( Molecular weight 383), 5-amino-1,3,8-naphthalene trisulfonic acid (molecular weight 383), 5-amino-1,4,8-naphthalene trisulfonic acid (molecular weight 383), 4-amino-1,6,6 7-naphthalene trisulfonic acid (molecular weight 383), 8-amino-1,3,5-naphthalene trisulfonic acid (molecular weight 383), 8-amino-1,2,5-naphthalene trisulfonic acid (molecular weight 383), 5 -Amino-1,2,3-naphthalene trisulfonic acid (molecular weight 383), 5-amino-1,2,4-naphthalene trisulfonic acid (molecular weight 383), 8-amino-1,2, -Naphthalene trisulfonic acid (molecular weight 383), 8-amino-1,2,3-naphthalene trisulfonic acid (molecular weight 383), 2-amino-1,3,4-naphthalene trisulfonic acid (molecular weight 383), 2- Amino-1,3,5-naphthalene trisulfonic acid (molecular weight 383), 2-amino-1,3,6-naphthalene trisulfonic acid (molecular weight 383), 2-amino-1,3,7-naphthalene trisulfonic acid (Molecular weight 383), 2-amino-1,3,8-naphthalene trisulfonic acid (molecular weight 383), 2-amino-1,4,5-naphthalene trisulfonic acid (molecular weight 383), 2-amino-1,4 , 6-Naphthalenetrisulfonic acid (molecular weight 383), 2-amino-1,4,7-naphthalenetrisulfonic acid (molecular weight 383), 2-amino-1,4,8-na Talentrisulfonic acid (molecular weight 383), 3-amino-1,2,8-naphthalenetrisulfonic acid (molecular weight 383), 3-amino-1,2,7-naphthalenetrisulfonic acid (molecular weight 383), 3-amino -1,2,6-naphthalene trisulfonic acid (molecular weight 383), 3-amino-1,2,5-naphthalene trisulfonic acid (molecular weight 383), 6-amino-1,2,5-naphthalene trisulfonic acid ( Molecular weight 383), 6-amino-1,3,5-naphthalene trisulfonic acid (molecular weight 383), 6-amino-1,4,5-naphthalene trisulfonic acid (molecular weight 383), 2-amino-1,6,6 7-naphthalene trisulfonic acid (molecular weight 383), 7-amino-1,3,8-naphthalene trisulfonic acid (molecular weight 383), 7-amino-1,2,8-naphthalene Trisulfonic acid (molecular weight 383), 6-amino-1,2,7-naphthalene trisulfonic acid (molecular weight 383), 6-amino-1,3,7-naphthalene trisulfonic acid (molecular weight 383), 7-amino- 1,4,6-naphthalene trisulfonic acid (molecular weight 383), 7-amino-2,3,6-naphthalene trisulfonic acid (molecular weight 383), 7-amino-1,2,6-naphthalene trisulfonic acid (molecular weight) 383), 6-amino-1,2,8-naphthalene trisulfonic acid (molecular weight 383), 6-amino-1,3,8-naphthalene trisulfonic acid, 7-amino-1,4,5-naphthalene trisulfone Acid (molecular weight 383), 3-amino-1,6,7-naphthalene trisulfonic acid (molecular weight 383), 7-amino-1,3,5-naphthalene trisulfonic acid (molecular weight 83), 7-amino-1,2,5-naphthalene trisulfonic acid (molecular weight 383), 6-amino-1,2,3-naphthalene trisulfonic acid (molecular weight 383), 6-amino-1,2,4 -Naphthalene trisulfonic acid (molecular weight 383), 7-amino-1,2,4-naphthalene trisulfonic acid (molecular weight 383), 7-amino-1,2,3-naphthalene trisulfonic acid (molecular weight 383), 8- Acetylamino-1,3,6-naphthalene trisulfonic acid (molecular weight 383), 8-hydroxy-1,3,6-naphthalene trisulfonic acid (molecular weight 384), 2-hydroxynaphthalene-3,6,8-trisulfone Acid, 1,3,5,7-naphthalene tetrasulfonic acid (molecular weight 448), 1,2,3-naphthalene trisulfonic acid (molecular weight 368), 1,2,4-naphthal Talentrisulfonic acid (molecular weight 368), 1,2,5-naphthalenetrisulfonic acid (molecular weight 368), 1,2,6-naphthalenetrisulfonic acid (molecular weight 368), 1,2,7-naphthalenetrisulfonic acid ( Molecular weight 368), 1,2,8-naphthalene trisulfonic acid (molecular weight 368), 1,3,5-naphthalene trisulfonic acid (molecular weight 368), 1,3,6-naphthalene trisulfonic acid (molecular weight 368), 1 , 3,7-naphthalene trisulfonic acid (molecular weight 368), 1,3,8-naphthalene trisulfonic acid (molecular weight 368), 1,4,5-naphthalene trisulfonic acid (molecular weight 368), 1,4,6- Naphthalene trisulfonic acid (molecular weight 368), 2,3,5-naphthalene trisulfonic acid (molecular weight 368), 2,3,6-naphthalene trisulfone Acid (molecular weight 368), and the like.

  It is also preferable to use anthracenesulfonic acid (molecular weight 258), anthraquinone-2-sulfonic acid, anthraquinone-1-sulfonic acid (molecular weight 288).

2-amino-1-naphthalenesulfonic acid (tobias acid molecular weight 223), 4-amino-1-naphthalenesulfonic acid (naphthoic acid molecular weight 223), 8-amino-1-naphthalenesulfonic acid (peric acid molecular weight 223), 2-amino-6-naphthalenesulfonic acid (brennaic acid molecular weight 223), 1-amino-5-naphthalenesulfonic acid (lorenzic acid molecular weight 223), 5-amino-2-naphthalenesulfonic acid (molecular weight 223), 1 1 amino group and 1 sulfone such as amino-6-naphthalenesulfonic acid (molecular weight 223), 6-amino-1-naphthalenesulfonic acid (molecular weight 223), 3-amino-1-naphthalenesulfonic acid (molecular weight 223) It is preferable to use naphthylamine sulfonic acid having an acid group in terms of good heat resistance and light resistance. Shii is intended.
Among these, 2-amino-1-naphthalenesulfonic acid (tobias acid) is particularly preferable.

  Furthermore, 2-hydroxy-6-naphthalenesulfonic acid (shefic acid molecular weight 224), 1-hydroxy-4-naphthalenesulfonic acid (nevir-winter-acid: NW acid molecular weight 224), 1-hydroxy-5-naphthalenesulfonic acid ( It is also preferable to use hydroxynaphthalenesulfonic acid having one hydroxyl group and one sulfonic acid group, such as L acid molecular weight 224) and 2-hydroxy-8-naphthalenesulfonic acid (croseinic acid molecular weight 224).

  Among them, an organic sulfonic acid having 2 to 3 sulfone groups is preferable in that the color developability is good and high brightness can be achieved. When there are 4 or more sulfonic acids, environmental stability deteriorates and changes with time are likely to occur. With one sulfonic acid, the basic dye and the counter compound react in a 1: 1 ratio, and color is generated when the main color is used. May be worse.

  In the case of an organic sulfonic acid having a molecular weight in the range of 200 to 250, even if there is one sulfonic acid group per molecule, the color development is not impaired because the molecular weight of the counter compound itself is small. .

  Examples of organic carboxylic acids include tetrachlorophthalic acid (molecular weight 304), palmitic acid (molecular weight 257), stearic acid (molecular weight 285), arachidic acid (molecular weight 313), behenic acid (molecular weight 341), lignoceric acid (molecular weight 369). Oleic acid (molecular weight 282), elaidic acid (molecular weight 282), erucic acid (molecular weight 339), nervonic acid (molecular weight 367), linoleic acid (molecular weight 280), galolenic acid (molecular weight 278), arachidonic acid (molecular weight 305) ), Α-linolenic acid (molecular weight 278), stearidonic acid (molecular weight 276), eicosapentaenoic acid (molecular weight 302), docosahexaenoic acid (molecular weight 328), and the like.

[Ethylenically unsaturated monomer (a-1) represented by general formula (21)]
As the monomer having a sulfonic acid group, it is preferable to use an ethylenically unsaturated monomer (a-1) represented by the following general formula (21) in terms of brightness and resistance.
Formula (21)
[In General Formula (21), R ¹ represents a hydrogen atom or a methyl group.
R ² represents a single bond or a divalent linking group,
A represents the general formula (22), and Y ⁺ represents an inorganic or organic cation. ]
General formula (22)

[In General Formula (22), R ⁴ represents an alkylene group which may have a substituent, and n is an integer of 1 to 20. ]

The R ² in the general formula (21), an optionally substituted alkylene group, an optionally substituted oxyalkylene group, an arylene group which may have a substituent, -CH ₂ - O—CH ₂ CH (R ³ ) O—, —CONH—R ⁵ —, or —COO—R ⁵ —, R ³ represents a monovalent alkyl group having 1 to 30 carbon atoms, R ⁵ Represents an alkylene group which may have a substituent, an oxyalkylene group which may have a substituent, or an arylene group which may have a substituent.

In the general formula (21), specific examples of the alkylene group which may have a substituent of R ² include a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, or , Octamethylene group, etc .;
In the general formula (21), specific examples of the oxyalkylene group which may have a substituent of R ² include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, an oxyhexamethylene group. A methylene group or an oxyoctamethylene group;
In the general formula (21), specific examples of the arylene group which may have a substituent of R ² include a phenyl group, a nonylphenyl group, a paracumylphenyl group, and the like;
In the general formula (21), specific examples of the monovalent alkyl group having 1 to 30 carbon atoms of R ³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, and nonyl group. Decyl group or dodecyl group, etc .;
However, it is not limited to these.

The monovalent alkyl group having 1 to 30 carbon atoms of R ³ is preferably a monovalent alkyl group having 1 to 18 carbon atoms, and more preferably a monovalent alkyl group having 8 to 18 carbon atoms. The reason is that an alkyl group having a small number of carbon atoms adversely affects heat resistance. Further, in the case of an alkyl group having a large number of carbon atoms, there is a concern that it may adversely affect the solubility in preparing a resin or a dye salt product.

In general formula (21), the alkylene group which may have a substituent of R ^5, an oxyalkylene group which may have a substituent, and an arylene group which may have a substituent include those represented by general formula (1) The alkylene group, the oxyalkylene group, and the arylene group described for R ² in () are included, but are not limited thereto.

As R ² in the general formula (21), among them, —CH ₂ —O—CH ₂ CH (R ³ ) O— having a branched C 8-18 long chain alkyl group is polymerizable, It is preferable for reasons of availability and heat resistance.

In general formula (21), A represents general formula (22).
The ethylenically unsaturated monomer (a-1) of the present invention is characterized in that A next to the sulfo group (SO3) is an alkylene oxide represented by the general formula (22) and has a sulfate group. . Usually, a resin having a carboxylic acid group or a sulfonic acid group is used, but the present inventors have found that a resin having a sulfuric acid group having a stronger acidity than a carboxy group or a sulfonic acid group is more than a carboxyl group or a sulfonic acid group. In particular, it was thought that salt formation was caused by a strong interaction with a basic dye to improve the heat resistance of the colored composition, and the present invention was achieved.

In the general formula (22), specific examples of the alkylene group which may have a substituent of R ⁴ include the alkylene groups described for R ³ in the general formula (1). The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 2 or 3 carbon atoms.

  Moreover, n in General formula (22) is an integer of 1-20, it is preferable that n is an integer of 2-15, and it is more preferable that n is an integer of 5-10.

The Y ⁺ component in the general formula (21) constituting the ethylenically unsaturated monomer represents an inorganic or organic cation, and any known one can be used without limitation. Specific examples of Y include hydrogen, alkali metals, alkaline earth metals, and ammonium compounds. At that time, the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. An ammonium compound is a compound in which NH ₄ ⁺ or its H is substituted with a hydrocarbon group or the like.

As an ethylenically unsaturated monomer (a-1) shown by General formula (21), what is marketed may be used, what was synthesize | combined suitably,
As a specific example,
A commercially available product of Daiichi Kogyo Seiyaku Co., Ltd., aqualon KH-10, KH-1025, or polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate such as KH-05;
Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate such as HS-10, HS-1025, BC-10, BC-20;
A commercially available product manufactured by Sanyo Chemical Industries, Ltd., sodium polyoxyalkylene sulfate methacrylate such as Eleminol RS-3000;
Examples include commercially available products manufactured by Nippon Emulsifier Co., Ltd., bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfates such as Antox MS-60, and the like.

  These ethylenically unsaturated monomers (a-1) represented by the general formula (21) may be used alone or in combination of two or more. Among these, Aqualon KH- 10, KH-05 can be preferably used.

(Resin having an anionic group in the side chain)
The resin having an anionic group in the side chain is preferably a copolymer obtained by using a monomer containing at least one sulfonic acid group and / or a carboxyl group as a monomer component, and contains at least one sulfonic acid group. A copolymer obtained using a monomer as a monomer component is more preferable.

  When preparing a coloring composition for a color filter containing the salt-forming compound of the present invention and exhibiting properties as a color filter, it is possible to use the same type of resin as the binder resin constituting the coloring composition for the color filter. desirable. Since a vinyl resin is preferably used as the binder resin, a vinyl resin is most preferable as a resin for obtaining a salt-forming compound.

  Moreover, as resin which has an anionic group in the side chain of this invention, vinyl resin containing the structural unit represented by following General formula (51) is preferable, and acrylic resin is used preferably especially.

General formula (51)

[In the general formula (51), R ₅₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
Q ¹ represents an alkylene group, an arylene group, —CONH—R ₅₂ —, —COO—R ₅₂ —, and R ₅₂ represents an alkylene group. P ^- is, -SO ₃ ^- represents a ^- or -COO. Y ¹⁺ represents an inorganic or organic cation. ]

In general formula (51), R ₁₅₁ , a hydrogen atom, or a substituted or unsubstituted alkyl group is represented. Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₅₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, R ₁ is most preferably a hydrogen atom or a methyl group.

In the general formula (51), acrylic site and P ^- component of Q connecting the alkylene group, an arylene _{group, -CONH-R 52 -, -} COO-R 52 - represents a. R ₅₂ represents an alkylene group, and may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group. Among these, —CONH—R ₅₂ — and —COO—R ₅₂ — are preferable because of polymerizability and availability.

The Y ¹⁺ component in the general formula (51) constituting the resin represents an inorganic or organic cation, and any known one can be used without limitation. Specific examples of Y ¹ include hydrogen, an alkali metal, an alkaline earth metal, and an ammonium compound. At that time, the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. The ammonium compound is NH ⁴⁺ or a compound in which H is substituted with a hydrocarbon group or the like.

  In order to obtain a vinyl resin containing a structural unit represented by the following general formula (51) which is a preferred embodiment of the present invention, a method of copolymerizing monomers having a sulfonic acid group and / or a carboxyl group as a monomer component Is mentioned.

  Specific examples of the monomer having a sulfonic acid group or a carboxyl group that can be used to obtain a vinyl resin containing the structural unit represented by the general formula (51), which is a preferred embodiment of the present invention, are shown below. A particularly preferable monomer is an ethylenically unsaturated monomer represented by the general formula (21).

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the monomer having a carboxylic acid anhydride group include maleic anhydride, And itaconic anhydride.

Monomers having sulphonic acid groups are monomers of the formula (IV) and their water-soluble salts, in particular alkali metal salts, such as potassium and very particularly preferably sodium and ammonium salts.
_{R 56 (R 57) C =} C (R 8) -X-SO 3 H (IV)
[Wherein, R ₅₆ , R ₅₇ and R ₅₈ independently represent -H, a linear or branched alkyl group having 1 to 12 C atoms, or a linear or branched C atom of 2 to 12 atoms. Monounsaturated or polyunsaturated alkenyl groups with the latter two groups being unsubstituted or substituted by one or more groups —NH ₂ , —OH or —COOH , —COOH or —COOR ₅₉ and R ₅₆ is XSO ₃ H; R ₅₉ is a saturated or unsaturated hydrocarbon having 1 to 12 straight or branched C atoms; , A single bond, — (CH ₂ ) n— wherein n = 1 to 4, phenylene, preferably 1,4-phenylene, —CH ₂ —O-phenylene (preferably 1,4), —CH ₂ —O— _{CH 2 -CH (OH) -CH 2} -, is k = 1 to 6 -COO- ( _{CH 2) k -, - CO} -NH-, m = 0~3 a is -CO-NH-CR'R '' - (CH 2) m or _{-CO-NH-CH 2 -CH (} OH) -CH _2- is; R ′ is —H, —CH ₃ or —C ₂ H ₅ and R ″ is —H or —CH ₃ . ]

Particularly advantageous among the monomers having sulfonic acid groups are the monomers of formula (IVa), (IVb) and / or (IVc).
_{H 2 C = CH-X-} SO 3 H (IVa)
_{H 2 C = C (CH 3} ) -X-SO 3 H (IVb)
HO ₃ S—X— (R ₁₀ ) C═C (R ₁₁ ) —X—SO ₃ H (IVc)
[Wherein, R ₁₀ and R ₁₁ independently of one another are —H, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ or —CH (CH ₃ ) ₂ , and X is a single group. bond, n = 1 to 4 of the - (CH ₂₎ n-, phenylene, preferably 1,4-phenylene, -CH ₂ -O- phenylene (preferably _{1,4), - CH 2 -O-} CH 2 - CH (OH) —CH ₂ —, k = 1 to 6 —COO— (CH ₂ ) k—, —CO—NH—, m = 0 to 3 —CO—NH—CR′R ″ — (CH ₂ ) m- or —CO—NH—CH ₂ —CH (OH) —CH ₂ —; R ′ is —H, —CH ₃ or —C ₂ H ₅ and R ″ is —H or -CH _3. ]

  Very advantageous sulfonic acid group-containing monomers are 1-acrylamide-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-acrylamide-2- Methylpropanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, 3-methacrylamide-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid (2-methyl-2-propene- 1-sulfonic acid), allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, styrenesulfonic acid, p-styrenesulfonic acid, vinylsulfonic acid, isoprene Sulfonic acid, 3-sulfopropyla Lilate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts and esters of the acids mentioned, alkali metal salts and alkaline earth metal salts It is advantageous to be in the form of Na salts and K salts.

  Particularly preferred monomers having sulfonic acid groups are 2-acrylamido-2-methyl-1-propanesulfonic acid, vinyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, and 2-sodium sulfoethyl methacrylate.

[Ethylenically unsaturated monomer (a-1) represented by general formula (21)]
As the monomer having a sulfonic acid group, it is preferable to use an ethylenically unsaturated monomer (a-1) represented by the following general formula (21) in terms of brightness and resistance.
Formula (21)

[In General Formula (21), R ¹ represents a hydrogen atom or a methyl group.
R ² represents a single bond or a divalent linking group,
A represents the general formula (22), and Y ⁺ represents an inorganic or organic cation. ]
General formula (22)
[In General Formula (22), R ⁴ represents an alkylene group which may have a substituent, and n is an integer of 1 to 20. ]

The R ² in the general formula (21), an optionally substituted alkylene group, an optionally substituted oxyalkylene group, an arylene group which may have a substituent, -CH ₂ - O—CH ₂ CH (R ³ ) O—, —CONH—R ⁵ —, or —COO—R ⁵ —, R ³ represents a monovalent alkyl group having 1 to 30 carbon atoms, R ⁵ Represents an alkylene group which may have a substituent, an oxyalkylene group which may have a substituent, or an arylene group which may have a substituent.

In the general formula (21), specific examples of the alkylene group which may have a substituent of R ² include a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, or , Octamethylene group, etc .;
In the general formula (21), specific examples of the oxyalkylene group which may have a substituent of R ² include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, an oxyhexamethylene group. A methylene group or an oxyoctamethylene group;
In the general formula (21), specific examples of the arylene group which may have a substituent of R ² include a phenyl group, a nonylphenyl group, a paracumylphenyl group, and the like;
In the general formula (21), specific examples of the monovalent alkyl group having 1 to 30 carbon atoms of R ³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, and nonyl group. Decyl group or dodecyl group, etc .;
However, it is not limited to these.

The monovalent alkyl group having 1 to 30 carbon atoms of R ³ is preferably a monovalent alkyl group having 1 to 18 carbon atoms, and more preferably a monovalent alkyl group having 8 to 18 carbon atoms. The reason is that an alkyl group having a small number of carbon atoms adversely affects heat resistance. Further, in the case of an alkyl group having a large number of carbon atoms, there is a concern that it may adversely affect the solubility in preparing a resin or a dye salt product.

In general formula (21), the alkylene group which may have a substituent of R ^5, an oxyalkylene group which may have a substituent, and an arylene group which may have a substituent include those represented by general formula (1) The alkylene group, the oxyalkylene group, and the arylene group described for R ² in () are included, but are not limited thereto.

As R ² in the general formula (21), among them, —CH ₂ —O—CH ₂ CH (R ³ ) O— having a branched C 8-18 long chain alkyl group is polymerizable, It is preferable for reasons of availability and heat resistance.

In general formula (21), A represents general formula (22).
The ethylenically unsaturated monomer (a-1) of the present invention is characterized in that A next to the sulfo group (SO3) is an alkylene oxide represented by the general formula (22) and has a sulfate group. . Usually, a resin having a carboxylic acid group or a sulfonic acid group is used, but the present inventors have found that a resin having a sulfuric acid group having a stronger acidity than a carboxy group or a sulfonic acid group is more than a carboxyl group or a sulfonic acid group. In particular, it was thought that salt formation was caused by a strong interaction with a basic dye to improve the heat resistance of the colored composition, and the present invention was achieved.

In the general formula (22), specific examples of the alkylene group which may have a substituent of R ⁴ include the alkylene groups described for R ³ in the general formula (1). The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 2 or 3 carbon atoms.

  Moreover, n in General formula (22) is an integer of 1-20, it is preferable that n is an integer of 2-15, and it is more preferable that n is an integer of 5-10.

The Y ⁺ component in the general formula (21) constituting the ethylenically unsaturated monomer represents an inorganic or organic cation, and any known one can be used without limitation. Specific examples of Y include hydrogen, alkali metals, alkaline earth metals, and ammonium compounds. At that time, the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. An ammonium compound is a compound in which NH ₄ ⁺ or its H is substituted with a hydrocarbon group or the like.

As an ethylenically unsaturated monomer (a-1) shown by General formula (21), what is marketed may be used, what was synthesize | combined suitably,
As a specific example,
A commercially available product of Daiichi Kogyo Seiyaku Co., Ltd., aqualon KH-10, KH-1025, or polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate such as KH-05;
Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate such as HS-10, HS-1025, BC-10, BC-20;
A commercially available product manufactured by Sanyo Chemical Industries, Ltd., sodium polyoxyalkylene sulfate methacrylate such as Eleminol RS-3000;
Examples include commercially available products manufactured by Nippon Emulsifier Co., Ltd., bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfates such as Antox MS-60, and the like.

  These ethylenically unsaturated monomers (a-1) represented by the general formula (21) may be used alone or in combination of two or more. Among these, Aqualon KH- 10, KH-05 can be preferably used.

[Other ethylenically unsaturated monomers]
Other ethylenically unsaturated monomers are not particularly limited as long as they can be radically polymerized with the ethylenically unsaturated monomer (a-1) represented by the general formula (21). Can be selected as appropriate. For example,

  Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 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 isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;

Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
Tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (
(Meth) acrylates having a heterocyclic ring such as (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. Having an aromatic ring (
(Meth) acrylates;

(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;

  Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (Meth) acrylates having a hydroxyl group such as mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or caprolactone adducts of these monomers (immol number is 1 to 5);

  Methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, Phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polypropylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol polypro Lenglycol mono (meth) acrylate, phenoxypolyethyleneglycol mono (meth) acrylate, methoxypolyethyleneglycol (meth) acrylate, n-butoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, 2-methoxyethyl (meth) (Meth) acrylates having an ether group such as acrylate and 2-ethoxyethyl (meth) acrylate;

  3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-hexyloxetane (Meth) acrylates having;

Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (
N-substituted (meth) acrylamides such as meth) acrylamide or acryloylmorpholine;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile;
Antioxidant unit-containing (meth) acrylates having a hindered amine skeleton such as 1,2,2,6,6, -pentamethylpiperidyl (meth) acrylate and 2,2,6,6, tetramethylpiperidyl (meth) acrylate;
Alternatively, a mixture thereof can be mentioned.

  Vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether can also be copolymerized with the monomer (a-1).

  As other ethylenically unsaturated monomers, those having a thermally crosslinkable functional group or an alkyl group are preferred from the viewpoints of polymerizability with the monomer represented by formula (21) and the heat resistance of the colored composition.

  The heat-crosslinkable functional group is not particularly limited as a suitable structure. For example, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a tertiary butyl group, an epoxy And ethylenically unsaturated monomers having a group, mercapto group, isocyanate group, allyl group, (meth) acryl, glycidyl group, and the like. Above all, from the viewpoint of storage stability and reactivity with other materials in the use of a coloring composition for a color filter, a hydroxyl group, a carboxyl group, an oxetanyl group, a tertiary butyl group, an isocyanate group, a (meth) acryl group, an epoxy group, A glycidyl group is preferable, and a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group are particularly preferable.

  As the ethylenically unsaturated monomer that can be used, those having a thermally crosslinkable functional group are preferable from the viewpoint of heat resistance. Although it is not particularly limited as a suitable structure, for example, hydroxyl group, carboxyl group, carboxylic anhydride, primary or secondary amino group, imino group, oxetanyl group, tertiary butyl group, epoxy group, mercapto group, isocyanate group, Examples thereof include ethylenically unsaturated monomers having an allyl group, (meth) acrylic group, glycidyl group and the like. Above all, from the viewpoint of storage stability and reactivity with other materials in the use of a coloring composition for a color filter, a hydroxyl group, a carboxyl group, an oxetanyl group, a tertiary butyl group, an isocyanate group, a (meth) acryl group, an epoxy group, A glycidyl group is preferable, and a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group are particularly preferable.

  Of the ethylenically unsaturated monomers having a hydroxyl group, hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are most preferred from the viewpoint of heat resistance.

  Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloyloxymethyl) 3-hexyloxetane and the like.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate, and the like.

  The isocyanate group in the present invention includes a blocked isocyanate group and can be preferably used. Under normal conditions, the blocked isocyanate group can protect the isocyanate group with other functional groups to suppress the reactivity of the isocyanate group, and can be deprotected by heating to regenerate the active isocyanate group. The isocyanate block body is shown.

  Examples of commercially available ethylenically unsaturated monomers having such a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, Showa Denko); Examples include 2- (0- [1′methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko).

  Examples of the ethylenically unsaturated monomer having a glycidyl group include a glycidyl (meth) acrylate group.

  A structure suitable as an alkyl group is not particularly limited, but for example, a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group, a lauryl group, a dodecyl group, or an isostearyl group is preferable. , Methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and isostearyl (meth) acrylate are preferable.

  As a method for obtaining a resin obtained by copolymerizing an ethylenically unsaturated monomer (a) containing an ethylenically unsaturated monomer (a-1) suitable for the present invention, free radical polymerization and living radical polymerization are used. A known method can be used.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329 (reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the polymerization. Although it does not specifically limit as an organic solvent, For example, methanol, ethanol, normal propanol, isopropanol, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol Monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  The ethylenically unsaturated monomer (a-1) represented by the general formula (21) suitable for the present invention is 10% by weight to 95% by weight based on the total weight of the ethylenically unsaturated monomer (a). % Is preferable, and more preferably 20% by weight to 60% by weight.

  When the weight of the ethylenically unsaturated monomer (a-1) represented by the general formula (1) is less than 10% by weight, the proportion of the cationic dye in which salt formation reaction occurs is low. Therefore, the amount of unformed salt cationic dye increases, and as a result, the solvent solubility is lowered and a phenomenon such as precipitation of foreign matters occurs. Further, in order to prevent the precipitation of foreign matters, it is necessary to increase the amount of solvent in the resist material, but this is not preferable because the coating property is remarkably deteriorated. On the other hand, when the content exceeds 95% by weight, a salt is formed into a resin obtained by radical polymerization of the ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (21). Since the amount of the cationic dye to be increased is too large, the heat resistance is deteriorated, which is not preferable.

  The molecular weight of the resin obtained by radical polymerization of the ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (21) used in the present invention is particularly Although not limited, it is preferable that the conversion weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000-500,000, and it is more preferable that it is 3,000-15,000. .

  In addition, a resin obtained by radical polymerization of an ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (21) suitable for the present invention is an organic solvent. A mixed solution may be used. As an organic solvent, methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol mono Chill ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone, and the like. Moreover, you may have the characteristic melt | dissolved in the propylene glycol monomethyl ether acetate etc. which are the solvent widely used for the coloring composition for color filters.

(Acid dyes)
Further, the hue can be controlled by using a counter compound as an acid dye.
Examples of the acid dyes include anthraquinone acid dyes, monoazo acid dyes, disazo acid dyes, oxazine acid dyes, amino ketone acid dyes, quinoline acid dyes, and triarylmethane acid dyes.

  More specifically, examples of the acid dye include C.I. I. Acid Yellow-11, C.I. I. Acid Yellow-23, C.I. I. Acid Green 3 (edible green No. 1), C.I. I. Acid Green 5 (edible green No. 2), C.I. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 19, C.I. I. Acid Green 25 and the like.

  In the case of an acid dye, a more preferable molecular weight range is 300 to 750. More preferably, it is the range of 350-700. By setting the molecular weight within this range, a colorant having a good balance between weather resistance and coloring power can be obtained, which is preferable.

[Salt making]
These salt-forming compounds of a basic dye and a counter compound can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
For example, after the triarylmethane basic dye is dissolved in water, an organic sulfonic acid or (sodium organic sulfonate) solution is added, and the chlorination treatment may be performed while stirring. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion of the triarylmethane basic dye and the sulfonic acid group (—SO ₃ H) portion of the organic sulfonic acid are bonded is obtained.
Here, the organic sulfonic acid can be dissolved in an alkali solution such as sodium hydroxide before the salt-forming treatment and used as a form of sodium sulfonate (—SO ₃ Na). In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

[Resin having an acid group]
The salt-forming compound [A1] used in the present invention further has an acid group such as a carboxyl group (rosin-modified maleic acid resin (also synonymous with rosin-modified fumaric acid resin)), rosin ester, polyester resin, and acid value. By adding a styrene acrylic copolymer or the like, the compatibility and dispersibility in the binder resin and the dispersibility in the solvent are greatly improved. As a result, the colorant, heat resistance, and light resistance are further improved as a colorant. Here, the acid group is preferably a carboxyl group (—COOH) or a sulfone group (—SO ₃ H).

The resin having an acid group preferably has a weight average molecular weight in the range of 400 to 12,000. More preferably, it is 400-6000, Most preferably, it is the range of 400-2000. By using the thing of this range, compatibility with a salt-forming compound becomes favorable and dispersion | distribution in a binder resin becomes favorable as a coloring agent.
Moreover, the measurement of the weight average molecular weight of resin which has an acid group here was performed on condition of the following.
Tetrahydrofuran (THF) was added to the specimen and allowed to stand for 12 hours, and then the THF solution of the specimen was filtered, and the molecular weight of the specimen dissolved in the filtrate was measured. The measurement was performed by gel permeation chromatography (GPC), and the molecular weight was calculated from a calibration curve prepared with standard polystyrene.
GPC device: HLC-8120GPC manufactured by Tosoh Corporation
Column: TSK Guardcolumn manufactured by Tosoh Corporation
Super-H-HT / SK-GEL / Super HM-M 3 flow rate: 1.0 ml / min (THF)

As the resin having an acid group, rosin-modified maleic acid resin is preferably used. The rosin-modified maleic resin has an acid-containing polar group portion and a non-polar rosin skeleton portion. The polar group portion having this acid is a carboxyl group portion derived from unreacted abietic acid and a carboxyl group of maleic acid, and reacts and is compatible with the polar group portion of the binder resin. Further, the nonpolar rosin skeleton part is compatible with the nonpolar part of the binder resin.
Moreover, the effect of the reaction between the acid component of the rosin-modified maleic resin and the amino group portion of the basic dye (unreacted basic dye in the salt-forming compound) is also great.

The acid value of the resin having an acid group is preferably in the range of 100 to 300 mgKOH / g. If the acid value is less than 100 mgKOH / g, the compatibility with the salt-forming compound is deteriorated. On the other hand, if the acid value is larger than 300 mgKOH / g, it becomes unfavorable because it causes poor developability when used as an alkali developing type colored resist described later.
Here, the acid value is a value measured by the method of JIS K-0070.

When a resin having an acid group is added to and mixed with the salt-forming compound (B) used in the present invention, it can be obtained by the following method.
(1) A method in which a salt-forming compound is added after being dissolved in a solvent soluble in a resin having an acid group and then mixed in the solution. (2) A resin having an acid group is melted using a kneader or the like. Examples thereof include a method of adding and mixing the salt-forming compound in the state of being prepared, but it may be synthesized by any conventionally known method.

  An example of these is as follows. Here, an example using a triarylmethane basic dye and a rosin-modified maleic resin is shown.

(1) Method of adding a salt-forming compound after being dissolved in a solvent soluble in a resin having an acid group and mixing in the solution (1-1)
After the triarylmethane basic dye is dissolved in water, a counter compound such as organic sulfonic acid is added, and a chlorination treatment is performed while stirring. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane basic dye and the acid group portion in the counter are bonded is obtained.
Here, the counter compound can be dissolved in an alkali solution such as sodium hydroxide before the salt-forming treatment and used in the form of sodium sulfonate (—SO ₃ Na). In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

(1-2)
Next, it is a step of adding a rosin-modified maleic acid resin. After adding an aqueous alkali solution such as an aqueous sodium hydroxide solution to adjust to neutral, the rosin-modified maleic acid resin dissolved in the aqueous alkali solution is added and stirred. Mix while mixing. Next, a rosin-modified maleic resin is insolubilized by adding a mineral acid such as hydrochloric acid or sulfuric acid to make it acidic, and then filtered, washed and dried to obtain a composition. Moreover, what is necessary is just to obtain a desired particle size through a grinding | pulverization process if necessary.

(2) Method of adding and mixing salt forming compound in melted resin having acid group using kneader or the like Salt forming compound (B) of the present invention and resin having acid group (rosin-modified maleic acid Resin etc.) into a kneader such as a heating kneader, Banbury mixer, 3-roll mill, 2-roll mill, vibration mill, ball mill, attritor, extruder, etc. Then, melt kneading is performed at a temperature equal to or higher than the softening point of the resin having an acid group. Thereby, the salt-forming compound is dispersed in the resin having an acid group. The composition obtained here is in a state where a salt-forming compound is coated with a resin having an acid group. Furthermore, the composition may be obtained by coarsely crushing and pulverizing the composition to adjust to a desired particle size.

The color mixing ratio of the salt-forming compound (B) of the present invention to the acid group-containing resin (salt-forming compound (B): acid group-containing resin) is in the range of 70:30 to 95: 5, so that good coloring is achieved. An agent can be obtained. If the ratio of the resin having an acid group is larger than 30% by weight, the color developability is deteriorated, that is, the color defect derived from the resin having an acid group is likely to occur, and the ratio of the resin having an acid group is 5% by weight. When it becomes smaller than this, the dispersibility improvement effect of the salt-forming compound in the binder resin becomes small.
More preferably, the weight mixing ratio of the salt-forming compound (B) of the present invention and the resin having an acid group (salt-forming compound: resin having an acid group) is in the range of 75:25 to 90:10.

  The preferable concentration of the basic dye (B) component is 0.1% by weight or more from the viewpoint of obtaining sufficient color reproducibility based on the total nonvolatile components (100% by weight) of the photosensitive coloring composition of the present invention. More preferably, it is 1.0% by weight or more, and most preferably 10% by weight or more. Further, since the stability of the photosensitive coloring composition is improved, the preferred concentration of the basic dye (B) component is 50% by weight or less, more preferably 40% by weight or less, and most preferably 30% by weight. It is as follows.

《Other colorants》
The colored composition for a color filter of the present invention can further contain other colorants in addition to the dye monomer (A) and the salt-forming compound (B). Other colorants are preferably blue pigments, purple pigments, or xanthene dyes other than the dye monomer (A).

  When the dye monomer (A) and the salt-forming compound (B) contain other colorants, the content of the other colorant is the same as that of the dye monomer (A) and the salt-forming compound (B). 1 to 300 parts by weight is preferable with respect to 100 parts by weight in total. More preferably, it is 25-200 weight part, More preferably, it is 50-100 weight part. When the amount of other colorant added is 1 part by weight or more and 300 parts by weight or less, the reproducible chromaticity region is widened, which is preferable.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

  In particular, when a colored composition is used for a blue filter segment, the spectral spectrum has a high transmittance in the vicinity of 425 to 500 nm having a characteristic peak of many backlights by using a blue pigment in combination. This is preferable because a high brightness can be obtained as a blue filter segment rather than a colorant combining a conventional blue pigment and other pigments.

  Examples of the green pigment include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

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

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like.
Examples of orange pigments that work in the same way as red pigments include C.I. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61 can be used. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 254, C.I. I. It is particularly preferable to use Pigment Red 177.

(Miniaturization of pigment)
When the colorant used in combination with the coloring composition of the present invention is a pigment, it can be refined by a salt milling treatment or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. If the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. If the thickness is larger than 90 nm, sufficient spectral characteristics may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling means mixing a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent into a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, etc. This is a treatment in which a water-soluble inorganic salt and a water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a machine. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions at the time of subjecting the pigment to salt milling, a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range can be obtained.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment, from both the processing efficiency and the production efficiency.

  The water-soluble organic solvent functions to wet 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 to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether Tellurium, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, diethylene glycol Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

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

  The content of the colorant is preferably in the range of 10 to 45% by weight, more preferably in the range of 15 to 40% by weight, based on the solid content of the color filter coloring composition. If it is this range, since the color reproducibility at the time of using a color filter in a general film thickness range (about 1.0-3.0 micrometers) is favorable, it is preferable.

<Photocationic polymerization initiator (A)>
The cationic photopolymerization initiator (A) generates a strong acid such as tetrafluoroboric acid or hexafluorophosphoric acid by UV irradiation or heating, and the strong acid protonates an oxygen atom of a cationically polymerizable compound described later to form a cationic active species. Is formed and the polymerization reaction is started, and any known compound can be used without particular limitation.

As the cationic photopolymerization initiator (A), for example, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thioxanthonium, (2,4-cyclopentadien-1-yl) [(1 -Methylethyl) benzene] -iron cation, or thianthrium, and the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or [BX ₄ ] ⁻ (where X is a phenyl group) An aromatic sulfonium salt (A1), an aromatic iodonium salt (B2), an aromatic diazonium salt, wherein two or more hydrogen atoms represent a functional group substituted with a fluorine atom or a trifluoromethyl group. , Aromatic ammonium salt, thioxanthonium salt, or (2,4-cyclopentadien-1-yl) [(1-methylethyl ) Benzene] - Iron These cationic photopolymerization initiators and the like salts can be used alone or in optionally two or more at an arbitrary ratio of one.

  Among these, the aromatic sulfonium salt (A1) or the aromatic iodonium salt (A2) is preferable for improving the remaining film ratio and adhesion, and more preferably the aromatic sulfonium salt from the viewpoint of improving the remaining film ratio. (A1).

  Examples of the aromatic sulfonium salt (A1) include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (Diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenyl) Ruthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- ( Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimony Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4 -(Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate and the like can be used.

  Examples of the aromatic iodonium salt (A2) include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and bis (dodecylphenyl) iodonium hexafluoro. Phosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) Phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1- Tilethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Etc. can be used.

  As the aromatic diazonium salt, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate and the like can be used.

  Examples of aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl- 2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl)- 2-Cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate, and the like can be used.

  Moreover, S-biphenyl 2-isopropyl thioxanthonium hexafluorophosphate etc. can be used as a thioxanthonium salt.

(2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene]. -Iron (II) hexafluorophosphate, (2,4-cyclopentadiene-1-
Yl) [(1-methylethyl) benzene] -iron (II) hexafluoroantimonate, 2
, 4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron (II) tetrafluoroborate, 2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron (II) Tetrakis (pentafluorophenyl) borate and the like can be used.

  Examples of the photocationic polymerization initiator (A) include CPI-100P, CPI-200K, CPI-101A (manufactured by San Apro Co., Ltd.), Syracure photocuring initiator UVI-6990, Syracure photocuring initiator UVI- 6992, Cyracure photocuring initiator UVI-6976 (above, manufactured by Dow Chemical Japan Co., Ltd.), Adeka optomer SP-150, Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172 (Asahi Denka Kogyo Co., Ltd.), CI-5102, CI-2855 (Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-145 Sun-Aid SI-150, Sun-Aid SI-160, Sun-Aid SI-180 (manufactured by Sanshin Chemical Industry Co., Ltd.), Esacure 1064, Esacure 1187 (manufactured by Lamberti), Omnicat 432, Omnicat 440, Omni Cat 445, Omni Cat 550, Omni Cat 650, Omni Cat BL-550 (manufactured by IG Resin), Irgacure 290, Irgacure 250 (manufactured by BASF Corp.), Rhodesil Photoinitiator 2074 (RHODORSIL PHOTOINITIATOR 2074 (Rhodia Japan) WPI-113, WPI-116, WPI-169, WPI-170 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like are commercially available.

  Among these, CPI-100P, CPI-101A, CPI-200K, CPI-210S, Irgacure 290, which is an aromatic sulfonium salt (A1), or Irgacure 250, which is an aromatic iodonium salt, WPI-113, WPI-116, WPI-169, and WPI-170 manufactured by Kojun Pharmaceutical Co., Ltd. are preferable.

  The content ratio of the cationic photopolymerization initiator (A) to the salt-forming compound (B) is preferably 0.1 to 40 parts by weight of the cationic photopolymerization initiator (A) with respect to 100 parts by weight of the salt-forming compound (B). More preferably, it is 0.1-30 weight part. When the content of the cationic photopolymerization initiator (A) is 0.1 parts by weight or more and 30 parts by weight or less, it is preferable because the heat resistance and solvent resistance are superior.

  The photocationic polymerization initiator (A) is preferably used in an amount of 0.1 to 30% by weight in a total of 100% by weight of the solid content of the color filter coloring composition, from the viewpoint of chemical resistance and transmittance. More preferably, it is used in an amount of 1 to 20% by weight.

<Photopolymerizable monomer>
The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce transparent resins include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and epoxy (meth). Acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, di Various acrylic esters such as enterythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate And methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile The effects of the present invention are not limited to these.

Moreover, the photopolymerizable monomer may contain an acid group. For example, esterified product of poly (meth) acrylates containing free hydroxyl group of polyhydric alcohol and (meth) acrylic acid and dicarboxylic acids; esterified product of polycarboxylic acid and monohydroxyalkyl (meth) acrylates, etc. Can be mentioned. Specific examples include monomethyl oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. And a monoesterified product of free carboxyl group with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. However, the effects of the present invention are not limited to these.
These photopolymerizable monomers can be used alone or in admixture of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 10 to 300 parts by weight and more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the colorant from the viewpoint of photocurability and developability. It is preferable.

<Photopolymerization initiator>
The colored composition of the present invention can be cured using radicals generated from the photopolymerization initiator by ultraviolet irradiation or heat irradiation. The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 150 parts by weight from the viewpoint of photocurability.

As the photopolymerization initiator, a conventionally known polymerization initiator can be used. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane , Oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenones such as phenyl] -2-methylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Examples include glyoxylic methyl ester. More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01, IRGACURE OXE-02 (BASF), Adekaoptomer N1717, Adekaoptomer N1919, Adeka Arcles NCI- 831 (ADEKA), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621, and Triazine derivatives described in JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, Japanese Patent Publication No. 47-1604 and diazonium compound publications described in US Pat. No. 3,567,453, USP No. 2,848,328, USP No. 2,852,379, and USP No. 2,940,853, organic azide compounds described in Japanese Patent Publication No. Sho 36- Ortho-quinonediazides described in JP-A-22062, JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610, JP-B-55-39162, JP-A-59-140203 And `` MACROMOLECULES '', No. Vol. 0, various onium compounds including iodonium compounds described on page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851 EP-A-126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986), metal allene complexes described in JP-A-61-151197. Transition metals such as ruthenium described in JP-A-2-182701, as well as the titanocenes described in Japanese Patent Publication No. 1993, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) Transition metal complexes, aluminate complexes described in JP-A-3-209477, JP-A-2-1577 No. 60, borate compounds, JP-A Nos. 55-127550 and 60-202437, 2,4,5-triarylimidazole dimers, carbon tetrabromide and JP-A No. Nos. 59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977. Aminoketone compounds described in JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, JP-T-2004-534797, JP-A-2006-342166 , JP2008-094770, JP2009-40762, 2010-15025, JP2010-189279, JP2010-189280, JP2010-526846, JP2010-527338, JP2010-527339, USP3558309 (1971), USP4202697 (1980) And oxime ester compounds described in JP-A No. 61-24558.
These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

<Antioxidant (E)>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  Examples of hindered phenol antioxidants include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (5,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (5,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (5,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (5,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, 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-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (5-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (5,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter because the brightness and sensitivity are good.

<Binder resin>
The binder resin is a material that disperses the colorant, particularly the dye monomer (A) and the pigment (B) of the present invention, or dyes and penetrates the dye monomer (A) of the present invention. Examples thereof include a plastic resin and a thermosetting resin.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. Furthermore, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used for the purpose of further improving photosensitivity and improving solvent resistance.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating film foreign matter is generated after the colorant is applied. The stability of the colorant is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the colorant is not easily trapped in the resin and the colorant mixture, and has a degree of freedom. The colorant component easily aggregates and precipitates, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the colorant is converted into a resin in a mixture of resin and colorant. Because it is easily trapped, it is difficult for the dye to elute in the solvent resistance test, the colorant component does not easily aggregate and precipitate, and the resin is three-dimensionally crosslinked when exposed to active energy rays to form a film. It is estimated that the colorant component is less likely to aggregate and precipitate even if the colorant molecules are fixed and the solvent is removed in the subsequent development step.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a coloring composition for a color filter, from the viewpoint of dispersibility, permeability, developability, and heat resistance of the dye monomer (A) and the pigment (B) of the present invention, a colorant. The balance of the adsorbing group and the carboxyl group that acts as an alkali-soluble group during development, the aliphatic group that acts as an affinity group for the colorant carrier and the solvent, and the aromatic group is important, and a resin having an acid value of 20 to 300 mgKOH / g is used. It is preferable to use it. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 30% by weight or more with respect to 100% by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500% by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, cardo resins, and phenol resins.

The thermosetting resin may be, for example, a low-molecular compound such as an epoxy compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, a cardo compound, and a phenol compound. It is not limited to this. By including such a thermosetting resin, the resin reacts at the time of firing the filter segment, the cross-linking density of the coating film is increased, the heat resistance is improved, and the effect of suppressing pigment aggregation at the time of firing the filter segment is obtained. It is done.
Among these, an epoxy resin, a cardo resin, or a melamine resin is preferable.

<Organic solvent>
In the coloring composition for a color filter of the present invention, a colorant is sufficiently dissolved in a monomer, a resin and the like, and applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm. In order to make it easier to form, a solvent can be included.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, 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 monotertiary 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, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, since the dye monomer (A) of the present invention has high solvent solubility, a wide variety of solvents from hydrophilic to hydrophobic can be used. Among them, alkyl lactates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, glycol acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and aromatic alcohols such as benzyl alcohol It is preferable to use ketones such as cyclohexanone.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types of mixed solvents, it is preferable that said preferable organic solvent contains 65 to 95 weight% in 100 weight% of the whole organic solvent.

  Moreover, since the organic solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the amount is 500 to 4000% by weight with respect to 100% by weight of the total weight of the colorant. It is preferable to use in.

<Sensitizer>
Furthermore, the colored photosensitive composition of the present invention can contain a sensitizer.
Sensitizers include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, teto Benzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran Examples thereof include, but are not limited to, derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, the dyes and sensitizers described in “Functional Materials” (1986, CMC), and other dyes and sensitizers that absorb light from the ultraviolet to the near infrared region. There may be mentioned sensitizers, and these may be used in an arbitrary ratio as required. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). Raised Although it is Rukoto, but is not limited thereto.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight with respect to 100% by weight of the total weight of the photopolymerization initiator (D) contained in the colored photosensitive composition. From the viewpoint of properties, it is more preferably 5 to 50% by weight.

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (5-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the weight (100% by weight) of the total solid content of the color filter coloring composition. . If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Amine compound>
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (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 amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to 100 weight% of thermosetting resins.

<Other additive components>
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on 100% by weight of the total amount of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (5, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (5,4-epoxycyclohexyl) methyltrimethoxysilane, β- (5,4-epoxycyclohexyl) ethyltriethoxysilane, β- (5,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, with respect to 100% by weight of the total amount of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition for a color filter of the present invention preferably comprises a coloring agent containing the coloring monomer (A) of the present invention in a coloring agent carrier comprising the resin and, if necessary, a solvent, preferably a coloring matter derivative or the like. In addition to the above dispersion aid, it can be produced by finely dispersing using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor.

  Moreover, the coloring composition for color filters of this invention can also be manufactured by mixing the pigment | dye monomer (A) of this invention, the other coloring agent separately disperse | distributed to the coloring agent support | carrier. Further, when the solubility of the dye monomer (A) of the present invention is high, specifically, it is highly soluble in the solvent to be used. There is no need to manufacture it in a dispersed manner.

[Dispersion aid]
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.

In the present invention, the dye monomer (A) of the present invention can also serve as a dispersion aid for the pigment used in combination.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more with respect to 100% by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40% by weight or less, and most preferably 35% by weight or less with respect to 100% by weight of the colorant.

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919 or Lactimon, Lactimon-WS or Bykumen, etc., SOLPERSE-3000, 9000, 1 manufactured by Lubrizol Japan 000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, manufactured by BASF Japan 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 456 , 4800,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight with respect to 100% by weight of the colorant. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment.
The color filter may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment, and the yellow filter segment is formed from the colored composition of the present invention. There may be.

  Preferably, at least one red or blue filter segment is formed using the coloring composition for a color filter of the present invention.

  As a base material such as a transparent substrate constituting the color filter, a glass plate such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. Used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

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

  A black matrix can be formed in advance before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

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

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

  First, a method for producing dye monomers, pigments, and binder resins used in Examples and Comparative Examples, a method for preparing a resin-type dispersant solution, a dye monomer / dispersion solution, a pigment dispersion, and a photosensitive coloring composition The manufacturing method and evaluation method of a thing are demonstrated.

<Method for producing acrylic resin solution>
First, a method for measuring the polymerization average molecular weight (Mw) and acid value of the resin will be described.
(Resin polymerization average molecular weight (Mw))
Polymerization average molecular weight (Mw) of the resin is TSKgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and measured in terms of polystyrene measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo Co., Ltd.) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

  Next, the binder resin used for the Example and the comparative example, and the manufacturing method of a salt-forming compound are demonstrated.

(Acrylic resin solution (R-1))
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed.
Next, the inside of the flask was purged with air, 0.3 parts of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when it reached 0.8, and a resin solution having a weight average molecular weight of about 12000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours, and propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20%. An acrylic resin solution (R-1) which is an energy ray curable resin having a bond was obtained.

<Method for producing salt-forming compound>
(Method for producing salt-forming compound B-1)
C. I. 12 parts of Basic Blue 7 (Tokyo Chemicals), 7.4 parts of sodium dodecyl sulfate (Tokyo Chemicals), 130 parts of dichloromethane and 200 parts of water were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with the 60 degreeC vacuum dryer, and obtained 14.7 parts of pigment | dyes (salt-forming compound B-1). The yield was 84.8%.

(Method for producing salt-forming compound B-2)
C. I. 20 parts of Basic Blue 7 (Tokyo Chemicals), 30.8 parts of “Aqualon KH-10” (trademark; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) which is a sulfate having a polymerizable unsaturated group and a polyoxyalkylene group, propylene 120 parts of glycol monomethyl ether acetate (PGMAC) and 100 parts of water were mixed and stirred at room temperature for 2 hours. Thereafter, the organic layer was extracted, washed with water, and the organic layer was concentrated under reduced pressure. And it dried with a 60 degreeC vacuum dryer, and obtained 40.0 parts pigment | dye (salt-forming compound B-2). The yield was 78.7%.

<Method for producing resist material>

[Example 1]
(Resist material (CR-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (CR-1).

Salt-forming compound B-1: 1.4 parts Photocationic polymerization initiator A-1: 0.07 parts (“Irgacure 290” manufactured by BASF Japan Ltd .:
Triarylsulfonium tetrakis- (pentafluorophenyl) borate)
Acrylic resin solution (R-1): 41.0 parts dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 6.0 parts Photopolymerization initiator: 0.6 parts (manufactured by BASF Japan “ "Irgacure OXE02")
Antioxidant ("Irganox 1010" manufactured by BASF Japan): 0.2 parts ("Irgaphos 168" manufactured by BASF Japan): 0.6 parts Propylene glycol monomethyl ether acetate: 50.13 parts

[Example 2]
(Resist material (CR-2))
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (CR-2).

Salt-forming compound B-1: 1.4 parts Photocationic polymerization initiator A-1: 0.14 parts (“Irgacure 290” manufactured by BASF Japan Ltd .:
Triarylsulfonium tetrakis- (pentafluorophenyl) borate)
Acrylic resin solution (R-1): 41.0 parts dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 6.0 parts Photopolymerization initiator: 0.6 parts (manufactured by BASF Japan “ "Irgacure OXE02")
Antioxidant ("Irganox 1010" manufactured by BASF Japan): 0.2 parts ("Irgaphos 168" manufactured by BASF Japan): 0.6 parts Propylene glycol monomethyl ether acetate: 50.06 parts

[Example 3]
(Resist material (CR-3))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (CR-3).

Salt-forming compound B-1: 1.4 parts Photocationic polymerization initiator A-1: 0.14 parts (“Irgacure 290” manufactured by BASF Japan Ltd .:
Triarylsulfonium tetrakis- (pentafluorophenyl) borate)
Acrylic resin solution (R-1): 41.0 parts dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 6.0 parts Photopolymerization initiator: 0.6 parts (manufactured by BASF Japan “ "Irgacure OXE02")
Propylene glycol monomethyl ether acetate: 50.86 parts

[Comparative Example 1]
(Resist material (CR-4))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain an alkali developing resist material (CR-4).

Salt-forming compound B-1: 1.4 parts acrylic resin solution (R-1): 41.0 parts dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 6.0 parts photopolymerization initiator : 0.6 part ("Irgacure OXE02" manufactured by BASF Japan)
Antioxidant ("Irganox 1010" manufactured by BASF Japan): 0.2 parts ("Irgaphos 168" manufactured by BASF Japan): 0.6 parts Propylene glycol monomethyl ether acetate: 50.2 parts

[Example 4]
(Resist material (CR-5))
A resist material (CR-5) was prepared in the same manner as the resist material (CR-1) except that the salt-forming compound B-1 was changed to the salt-forming compound B-2.

[Example 5]
(Resist material (CR-6))
A resist material (CR-6) was prepared in the same manner as the resist material (CR-2) except that the salt-forming compound B-1 was changed to the salt-forming compound B-2.

[Example 6]
(Resist material (CR-7))
A resist material (CR-7) was prepared in the same manner as the resist material (CR-3) except that the salt-forming compound B-1 was changed to the salt-forming compound B-2.

[Comparative Example 2]
(Resist material (CR-8))
A resist material (CR-8) was prepared in the same manner as the resist material (CR-4) except that the salt-forming compound B-1 was changed to the salt-forming compound B-2.

<Evaluation of coloring composition>
About the obtained resist material (CR-1-8), the heat resistance test was done with the following method.

(Evaluation of heat resistance)
A resist material was applied on a glass substrate so that y = 0.090 in a C light source, and a substrate was produced. The brightness (Y1) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Thereafter, the substrate was heated at 230 ° C. for 60 minutes, and the brightness (Y2) was measured again. A value obtained by dividing Y2 by Y1 at this time was used as an index of heat resistance. The evaluation criteria are as follows.
◎ ... 0.93 or more ○ ・ ・ ・ 0.85 or more and less than 0.93 Δ ... 0.75 or more and less than 0.85 × ... 0.75 or less

  The resist materials (CR-1 to 3) and (CR-5 to 7) of the present invention containing the cationic photopolymerization initiator A-1 are compared to the resist materials (CR-4) and (CR-8) not containing the resist materials. , Both improved heat resistance.

  From the above results, the colored composition for color filters of the present application can provide a coating film that not only has excellent lightness but also excellent heat resistance and solvent resistance. It was confirmed that the filter could be provided.

Claims (7)

A color filter comprising a colorant comprising a salt-forming compound (B) of a triarylmethane basic dye and a counter compound having an anionic group, a binder resin, a solvent, and a photocationic polymerization initiator (A) A coloring composition for color filters , wherein the cationic photopolymerization initiator (A) contains an aromatic sulfonium salt (A1) . Salt-forming counter of Compound (B) is an organic sulfonic acid or a metal salt or a color filter for coloring composition according to claim 1, wherein a in the side chain is a resin having an anionic group. The coloring composition for a color filter according to claim 2, wherein the organic sulfonic acid or a metal salt thereof is represented by the following general formula (11).
Formula (11)
[In General Formula (11), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, and M + each independently represents a hydrogen ion or a metal ion. n represents an integer of 1 to 4. ] The coloring composition for a color filter according to claim 2, wherein the organic sulfonic acid or a metal salt thereof is an ethylenically unsaturated monomer (a-1) represented by the general formula (21).
Formula (21)
[In General Formula (21), R ¹ represents a hydrogen atom or a methyl group.
R ² represents a single bond or a divalent linking group,
A represents the general formula (22), and Y ⁺ represents an inorganic or organic cation. ]
General formula (22)
[In General Formula (22), R ⁴ represents an alkylene group which may have a substituent, and n is an integer of 1 to 20. ] Furthermore, the coloring composition for color filters of any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator. Furthermore, antioxidant is included, The coloring composition for color filters of any one of Claims 1-5 characterized by the above-mentioned. A color filter comprising a filter segment formed from the colored composition for a color filter according to any one of claims 1 to 6 on a substrate.