JP6357850B2 - 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 a dye monomer having a specific structure, a triarylmethane basic dye, and a counter compound having an anionic group It has been found that high brightness can be achieved by including a salt-forming compound (B) comprising: and that excellent performance can be achieved with respect to heat resistance and light resistance.

  That is, this invention is a coloring composition for color filters containing a coloring agent, binder resin, and a solvent, Comprising: This coloring agent is a pigment monomer (A) represented by following General formula (1). And a salt-forming compound (B) of a triarylmethane basic dye and a counter compound having an anionic group (except for the case of a dye monomer (A)). It is related with the coloring composition for filters.

[In General Formula (1), Q represents an organic dye skeleton.
X is a direct _{bond, -R 2 -, - NH-} R 3 -, - O-R 3 -, - CO-R 3 -, - COO-R 3 -, or -O-CO-R ₃ - represents a .
R ₁ represents a hydrogen atom or a methyl group.
R ₂ represents a substituted or unsubstituted alkylene group, an alkylene group containing at least one bond selected from a substituted or unsubstituted ester bond (—COO—) or an ether bond (—O—), substituted or unsubstituted, unsubstituted alkenylene group, a substituted or unsubstituted arylene _{group, -R 4 -O-R 5 -} , - R 4 -CO-R 5 -, - R 4 -COO-R 5, -R 4 -O-CO —R ₅ —, —R ₄ —O—CONH—R ₅ —, or —R ₄ —O—CO—R ₆ —CO—R ₅ — is represented.
R ₃ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, —R ₄ —O—R ₅ —, —R ₄ —CO—R ₅ —, —R _{4 -O-CO-R 5 -} , - R 4 -O-CONH-R 5 -, or _{-R 4 -O-CO-R 6} -CO-R 5 - represents a.
R ₄ and R ₆ each independently represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.
R ₅ represents a substituted or unsubstituted alkylene group, or —O—CH ₂ —CHOH—CH ₂ —. ]

  In the present invention, the organic dye skeleton Q in the general formula (1) is a xanthene dye skeleton represented by the following general formula (2), an anthraquinone dye skeleton represented by the following general formula (3-1), An anthraquinone dye skeleton represented by the formula (3-2), an anthraquinone dye skeleton represented by the following general formula (3-3), a triarylmethane dye skeleton represented by the following general formula (4-1), and The present invention relates to the coloring composition for a color filter, which is at least one organic dye skeleton selected from the group consisting of a triarylmethane dye skeleton represented by the general formula (4-2).

[In general formula (2),
R _{31 to} R ₃₄ each independently represents a hydrogen atom or a monovalent substituent, and R ₃₁ and R ₃₂ , and R ₃₃ and R ₃₄ may form a ring structure.
R ₃₅ each independently represents a monovalent substituent, and m represents an integer of 0 to 5.
Y ⁻ represents an inorganic or organic anion.
Here, any one of R _{31 to} R ₃₅ is a bond with X. ]

[In the general formulas (3-1), (3-2), and (3-3),
R ₄₁ is a hydrogen atom, -ROH (R is an alkylene group having 1 to 5 carbon atoms), - RCOOH (R is an alkylene group having 1 to 5 carbon atoms) represents a phenyl group which may have a or substituent.
R _{42 to} R ₄₈ are each independently a hydrogen atom, a hydroxyl group, —NHR ₄₉ (R ₄₉ and R ₄₁ have the same meaning), an SO ₃ M group (M is a hydrogen ion or a metal ion), a halogen atom, —COR. '(R' represents an alkyl group having 1 to 3 carbon atoms).
Here, any one of R _{41 to} R ₄₈ is a bond with X. ]

[In the general formulas (4-1) and (4-2),
R ₂₁₁ , R ₂₁₂ , R ₂₁₃ , R ₂₁₄ , R ₂₃ , and R ₂₄ each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituent. Represents a good phenyl group, or adjacent Rs are bonded to form a ring.
R ₂₂ , R ₂₅ , and R ₂₆ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted group having 2 to 6 carbon atoms. It represents an alkenyl group, an optionally substituted phenyl group, an optionally substituted amino group, or a fluorine atom.
Y ⁻ represents an inorganic or organic anion.
Here, any one of R _{211 to} R ₂₁₄ and R _{22 to} R ₂₆ is a bond with X. ]

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

  The present invention also relates to the coloring composition for a color filter, wherein the sulfate ester or a metal salt thereof is represented by the following general formula (11).

[In general formula (11), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group,
M ⁺ each independently represents a hydrogen ion or a metal ion.
n represents an integer of 1 to 4. ]

  In addition, the present invention relates to the colored composition for a color filter, wherein the sulfate ester or a metal salt thereof is an ethylenically unsaturated monomer (a-1) represented by the general 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),
Y ⁺ represents an inorganic or organic cation. ]

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

In addition, the present invention relates to the coloring composition for a color filter, wherein the fluorine group-containing boron anion compound has an anion represented by the following general formula (31).

[In general formula (31),
R ^{12 to} R ¹⁵ each independently represents an alkyl group which may be substituted with a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom or an aryl group which may be substituted with a fluorine atom;
At least one of R ^{12 to} R ^{15 represents} an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, it excludes when R < ¹² > -R < ¹⁵ > is all fluorine atoms. ]

The present invention also relates to the color composition for color filters, wherein at least one of R ^{12 to} R ¹⁵ has a structure represented by the general formula (32).

[In general formula (32),
R ^{16 to} R ²⁰ each independently represent a hydrogen atom or a fluorine atom.
However, when R ¹⁶ to R ²⁰ are all hydrogen atoms is excluded. ]

  The present invention further relates to the coloring composition for a color filter, further comprising a phthalocyanine dye (except for the case of the pigment monomer (A)).

  The present invention further relates to the color composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention further relates to the coloring composition for a color filter, further comprising an antioxidant.

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

  The colored composition for a color filter of the present invention includes a pigment monomer having a specific structure and a specific salt-forming compound, 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 color filter coloring composition of the present invention is a color filter coloring composition containing a colorant, a resin, and a solvent, wherein the colorant is a dye monomer represented by the general formula (1). And (A) and a salt-forming compound (B) comprising a triarylmethane-based basic dye and a counter compound having an anionic group.
First, 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 includes, as a colorant, a pigment monomer (A) represented by the general formula (1), a triarylmethane basic dye, and a counter compound having an anionic group. And a salt-forming compound (B). By including these colorants, the solubility in an organic solvent is good, and the fastness such as heat resistance is also excellent.

  The content ratio of the dye monomer (A) and the salt-forming compound (B) is preferably 1 to 80 parts by weight of the dye monomer (A) with respect to 100 parts by weight of the salt-forming compound (B). More preferably, it is 10 to 40 parts by weight. When the content of the dye monomer (A) is 1 part by weight or more and 80 parts by weight or less, it is preferable because the heat resistance and the solvent resistance are excellent.

<< Dye monomer (A) >>
The dye monomer (A) is a dye represented by the general formula (1). A pigment monomer containing such a (meth) acryloyl group has improved solubility in organic solvents than ordinary dyes, and also contributes to improved fastness such as heat resistance. Suitable as a product.

In general formula (1), Q represents an organic dye skeleton.
X is a direct _{bond, -R 2 -, - NH-} R 3 -, - O-R 3 -, - CO-R 3 -, - COO-R 3 -, or -O-CO-R ₃ - represents a .
R ₁ represents a hydrogen atom or a methyl group.
R ₂ represents a substituted or unsubstituted alkylene group, an alkylene group containing at least one bond selected from a substituted or unsubstituted ester bond (—COO—) or an ether bond (—O—), substituted or unsubstituted, unsubstituted alkenylene group, a substituted or unsubstituted arylene _{group, -R 4 -O-R 5 -} , - R 4 -CO-R 5 -, - R 4 -COO-R 5, -R 4 -O-CO —R ₅ —, —R ₄ —O—CONH—R ₅ —, or —R ₄ —O—CO—R ₆ —CO—R ₅ — is represented.
R ₃ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, —R ₄ —O—R ₅ —, —R ₄ —CO—R ₅ —, —R _{4 -O-CO-R 5 -} , - R 4 -O-CONH-R 5 -, or _{-R 4 -O-CO-R 6} -CO-R 5 - represents a.
R ₄ and R ₆ each independently represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.
R ₅ represents a substituted or unsubstituted alkylene group, or —O—CH ₂ —CHOH—CH ₂ —.

  The “substituent” in the present invention includes a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, and trifluoromethyl. Monovalent to trivalent metal salt of an acidic group selected from a group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group (For example, sodium salt, potassium salt, aluminum salt, etc.). Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, an o-triphenyl group. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 In addition to -methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group and 2-methyl-4-sulfophenyl group, However, the organic dye skeleton Q is not limited thereto.

Examples of the substituted or unsubstituted alkylene group in R _{2 to} R ₆ include the following substituted or unsubstituted alkyl groups, linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 30 carbon atoms, or carbon A linear, branched, monocyclic or condensed polycyclic alkyl having 2 to 30 and containing at least one bond selected from an ester bond (—COO—) and an ether bond (—O—) Examples thereof include a divalent group formed by removing one hydrogen atom from a group.

  Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, 2-hexyldecyl group, sec-butyl group, tert-butyl group, sec -Pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, etc. However, it is not limited to these.

Specific examples of linear and branched alkyl groups having 2 to 30 carbon atoms and containing at least one bond selected from an ester bond (—COO—) and an ether bond (—O—) , —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 -CH 2 -CH 2 -O-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) 2, -CH 2 -O-CH 3, -CH 2 -CH 2 —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is from 1 to 8) Is an integer), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is an integer from 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH _{2. -CH 3 -, - CH 2 -CH-} (OCH 3) 2, -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 3, -CH 2 -CH 2 -CH 2 -O-CO-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) -CH 2 -CH 2 -CH 2 -CH It is given a _3, etc. It is, but is not limited thereto.

  Specific examples of monocyclic or condensed polycyclic alkyl groups having 2 to 30 carbon atoms and optionally containing at least one bond selected from an ester bond (—COO—) and an ether bond (—O—) Can include the following, but is not limited thereto.

Examples of the substituted or unsubstituted alkenylene group in R _{2 to} R ₆ include the following substituted or unsubstituted alkenyl groups, 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 vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopenta Examples thereof include, but are not limited to, a divalent group formed by removing one hydrogen atom from a dienyl group.

The substituted or unsubstituted arylene group in R _{2 to} R ₆ is a monocyclic or condensed polycyclic aromatic group that may contain a substituted or unsubstituted heteroatom having 6 to 30 carbon atoms, such as a phenyl group 1-naphthyl group, 2-naphthyl group, p-biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2-pyrenyl group, 3-perylenyl group, terphenyl group, thienyl group, benzothienyl group, naphthothienyl group, furyl group, pyranyl group, pyrrolyl group, imidazolyl A divalent group formed by removing one hydrogen atom from a group, pyridyl group, indole group, thiazole group, etc. It is, but is not limited thereto.

Moreover, the hydrogen atom of the substituted or unsubstituted alkylene group, alkenylene group, and arylene group in R _{2 to} R ₆ may be further substituted with another substituent.

  Such substituents include halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aryl groups, nitro groups, hydroxyl groups, substituted or unsubstituted alkoxyl groups, substituted Or an unsubstituted aryloxy group is mentioned.

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

X is preferably a direct bond, —R ₂ —, —O—R ₃ —, or —COO—R ₃ —, and is a direct bond, an unsubstituted alkylene group, —COO—R ₃ — (R ₃ is More preferably, the alkylene group has 1 to 5 carbon atoms), or -R ₄ —O—R ₅ — (wherein R ₄ and R ₅ are each independently an alkylene group having 1 to 5 carbon atoms).

(Organic dye skeleton Q)
There is no restriction | limiting in particular as organic pigment | dye frame | skeleton * Q in General formula (1), The various thing containing a well-known pigment | dye structure is applicable. Known dye structures include, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane). Dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, Croconium dyes), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, ni Nitroso pigments, and the like dye structure derived from a dye selected from those of the metal complex dye and the like.
Among these dye structures, azo dyes, dipyrromethene dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes from the viewpoint of color characteristics such as hue, color separation, and color unevenness. A dye structure derived from a dye selected from a dye and a subphthalocyanine dye is preferred, and is derived from a dye selected from an anthraquinone dye, triphenylmethane dye, xanthene dye, cyanine dye, squarylium dye, quinophthalone dye, phthalocyanine dye, and subphthalocyanine dye. A dye structure is most preferred. For specific pigment compounds that can form a pigment structure, “New Edition Dye Handbook” (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), “Color Index” (The
Society of Dyers and colorists), “Dye Handbook” (Okawara et al .; Kodansha, 1986).

Among these, Q is preferably an organic dye skeleton selected from the group consisting of xanthene, anthraquinone, and triarylmethane.
As these organic pigments, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. may be used. Direct dyes, oil-soluble dyes, and basic dyes are preferably used because they are excellent in reactivity and can easily produce the dye monomer (A).

  Among organic pigment skeletons such as xanthene dyes, anthraquinone dyes, and triarylmethane dyes, Q is a xanthene dye skeleton represented by general formula (2), general formulas (3-1) to (3-3). ), An anthraquinone dye skeleton represented by formula (IV), and a triarylmethane dye skeleton represented by formulas (4-1) and (4-2). And the contrast ratio is preferable. More preferred is a xanthene dye skeleton.

<Xanthene dye skeleton>
The xanthene dye skeleton is a dye skeleton containing a xanthene ring, and is mainly used for acidic forms containing hydroxyl groups (fluorescein), basic forms containing amino groups (rhodamines), and mixed systems (rhodols). Separated. Most of them belong to basic dyes or acid dyes and have a remarkably clear color tone. Of these, a rhodamine dye skeleton is preferable in terms of color tone.

  Among the xanthene dye skeletons, the xanthene dye skeleton represented by the general formula (2) is preferable because of excellent lightness and resistance.

In general formula (2),
R _{31 to} R ₃₄ each independently represents a hydrogen atom or a monovalent substituent, and R ₃₁ and R ₃₂ , and R ₃₃ and R ₃₄ may form a ring structure.
R ₃₅ each independently represents a monovalent substituent, and m represents an integer of 0 to 5.
Y ⁻ represents an inorganic or organic anion.
Here, any one of R _{31 to} R ₃₅ is a bond with X.

  The monovalent substituent in the general formula (2) is represented by the following substituent group A.

"Substituent group A"
Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups , Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonyl Amino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl group Or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphini Examples include a ruamino group and a silyl group. Details are described below.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms, or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl Or group of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

  Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Oct-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Le group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydro Sill group, a nitro group, a carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having a carbon number of 2 30 substituted or unsubstituted heterocyclic oxy groups, wherein the heterocyclic moiety is Preferably heterocyclic portion described in cyclic group, for example, 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino A sulfonylamino), alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonylami , Butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Base Yes, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms) And, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenylazo, p Chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide and N-phthalimide) A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably substituted having 2 to 30 carbon atoms) Or an unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

  Among the substituents of the substituent group A, those having a hydrogen atom may be further substituted at the hydrogen atom portion in the functional group. Examples of functional groups that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Specifically, methylsulfonylaminocarbonyl, Examples include p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

In the general formula (2), R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ , and R _{35 in} the case where m is 2 or more are each independently bonded to each other to form a 5-, 6-, or 7-membered saturation. A ring or a 5-membered, 6-membered or 7-membered unsaturated ring may be formed. For example, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring Preferably, a benzene ring and a pyridine ring are mentioned. When the formed 5-membered, 6-membered or 7-membered ring is a further substitutable group, it may be substituted with the above-mentioned substituent group A, and may be substituted with two or more substituents. The substituents may be the same or different.

In particular, R ₃₂ and R ₃₃ are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₃₁ and R ₃₄ are preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group.
R ₃₅ is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group. The substituent that the phenyl group of R ₃₁ and R ₃₄ has is most preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.

Bond and X is preferably R _35.

  Specific examples of xanthene dyes that can be used as a precursor of a dye monomer having a xanthene dye skeleton include the following acidic dyes, oil-soluble dyes, basic dyes, and the like. It is not a thing.

[Xanthene acid dyes]
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

[Xanthene oil-soluble dye]
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, or CI Solvent Violet 10 or the like.

  Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

[Xanthene-based basic dyes]
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B), 11 etc. are mentioned. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10, 11 are preferably used.

[Counter anion Y ⁻ ]
Y < ^- > represents an inorganic or organic anion, and any one having an anion ion can be used.
Typical examples include carboxylate ions, halide ions (chloride ions, bromide ions, etc.), triflate ions, sulfate ions, organic sulfonate ions (for example, alkyl sulfonates having 1 to 20 carbon atoms, benzene sulfonates, etc.), fatty acid ions. (C1-C20 aliphatic carboxylate, etc.), benzoate ion, oxalate ion, perhalogenate ion, thiocyanate ion, fluorine group-containing phosphorus anion, fluorine group-containing boron anion, cyano group-containing nitrogen anion, sulfone Examples thereof include an acid group-containing nitrogen anion or an anion having a conjugate base of an organic acid having a halogenated hydrocarbon group, and can be preferably used.

Alternatively, resins having these anionic groups in the side chain can be used, and among these resins, resins having an anion moiety of —SO ₃ ^— or —COO ^— are preferable. As such a resin, a resin having an anionic group in the side chain described as a counter compound of the salt-forming compound (B) described later can also be used.

  Moreover, the anionic compound described with the counter compound which can be used for salt formation of the salt-forming compound (B) mentioned later can also be used.

These anions Y ^- Among, in terms of resistance-conferring, having a sulfate ion, organic sulfonate ion, a sulfonic acid group-containing nitrogen anion, the conjugate base of an organic acid having a fluorine-containing boron anion or a halogenated hydrocarbon group, Anions are preferred.
More preferred is an anion having a conjugate base of an organic acid having a sulfate ion, a sulfonic acid group-containing nitrogen anion, a fluorine group-containing boron anion, or a halogenated hydrocarbon group.

More preferably,
The sulfate ion is a sulfate represented by the general formula (11) or the general formula (12) or a metal salt thereof,
As the fluorine group-containing boron anion, B (CN) ₃ F ⁻ , (CF ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻
An anion having a conjugate base of an organic acid having a halogenated hydrocarbon group is sulfonimidic acid (—SO ₂ NHSO ₂ —).

Although the specific example of the anion which can be used is described below, it is not limited to this.
Fluorine group-containing phosphorus anions include PF ₆ ⁻ , (CF ₃ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF ^{_{] 2 PF 4 -, [(}} CF 3) 2 CF] 3 PF 3 -, (n-C 3 F 7) 2 PF 4 -, (n-C 3 F 7) 3 PF 3 -, (n-C 4 F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ _{, (n-C 4 F 9} ) 2 PF 4 -, (n-C 4 F 9) 3 PF 3 -, (C 2 F 4 H) (CF 3) 2 PF 3 -, (C 2 F 3 H 2 ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ^{— and the} like.
Among these, PF ₆ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , ((n-C ₃ F ₇ ) ₃ PF ₃ ⁻ , (n-C ₄₎ F ₉ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , [( CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^— is preferred.

Specific examples of the fluorine-containing boron anion include BF ₄ −, (CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B (CN ) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F ₅ ) ₃ B (CN) ⁻ , (C ^{_{2 F 5) 2 B (CN}} ) 2 -, (n-C 3 F 7) 3 B (CN) -, (n-C 4 F 9) 3 B (CN) -, (n-C 4 F 9) ^{_{2 B (CN) 2 -,}} (n-C 6 F 3) 3 B (CN) -, (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, (CH 2 CF ^{_{3) 3 B (CN) -}} , (CH 2 CF 3) 2 B (CN) 2 -, (CH 2 C 2 F 5) 3 B (CN) -, (CH 2 C 2 F 5) 2 B (CN ^{_{) 2 -, (CH 2 CH}} 2 C 3 F 7) 2 B (CN) 2 -, (n-C 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN ) ^-, and the like.
Among these, B (CN) ₃ F ⁻ , (CF ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , and [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ are preferable.

As the cyano group-containing nitrogen anion, [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF ^{_{3 CF 2 SO 2)] -}} , [(FSO 2) N {(CF 3) 2 CFSO 2}] -, [(FSO 2) N (CF 3 CF 2 CF 2 SO 2)] -, [(FSO 2 ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ⁻ , [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like.

The conjugate base of the organic acid having a halogenated hydrocarbon group is not particularly limited, but examples of the organic acid having a halogenated hydrocarbon group include sulfonic acid having a halogenated hydrocarbon group (-SO ₃ H), sulfonimide acid (—SO ₂ NHSO ₂ —) and the like.

<Anthraquinone dye skeleton>
The anthraquinone dye skeleton is not limited as long as it has an anthraquinone skeleton, but the anthraquinone dye skeleton having a diaminoanthraquinone skeleton has color resistance, color reproducibility, and high brightness while having heat resistance and light resistance. It is preferable in terms of presentation. The reason why these are excellent in heat resistance and light resistance is presumed that the structure is stabilized by bonding the carbonyl group part of the anthraquinone skeleton and the amino group part with a hydrogen bond.

  Among the anthraquinone dye skeletons, the anthraquinone dye skeletons represented by the general formulas (3-1), (3-2), and (3-3) are preferable because they are excellent in lightness and resistance.

In the general formulas (3-1), (3-2), and (3-3), R ₄₁ is a hydrogen atom, —ROH (R is an alkylene group having 1 to 5 carbon atoms), —RCOOH (R is a carbon number) 1 to 5 alkylene groups) or a phenyl group which may have a substituent. R _{42 to} R ₄₈ are each independently a hydrogen atom, a hydroxyl group, —NHR ₄₉ (R ₄₉ and R ₄₁ have the same meaning), an SO ₃ M group (M is a hydrogen ion or a metal ion), a halogen atom, —COR. '(R' represents an alkyl group having 1 to 3 carbon atoms). Here, any one of R _{41 to} R ₄₈ is a bond with X.

In the general formulas (3-1), (3-2), and (3-3), R ₄₁ is —ROH (wherein R is an alkylene group having 1 to 5 carbon atoms), —RCOOH (where R is 1 carbon atom). ~ 5 alkylene group), and a phenyl group which may have a substituent. R _{42 to} R ₄₈ are preferably each independently a hydrogen atom, a halogen atom, or an alkoxy group.

The bond to X is preferably either R ₄₁ or R ₄₈ , and more preferably R ₄₁ .

  M is a hydrogen ion or a metal ion. Examples of metal ions include alkali metal ions and alkaline earth metal ions, and specific examples include sodium ions, potassium ions, lithium ions, calcium ions, and magnesium ions.

  Examples of the “substituent” that the alkylene group, halogen atom, alkyl group, and alkoxy group in the general formulas (3-1), (3-2), and (3-3) can have include the xanthene dye skeleton. This is the same as “Substituent group A” mentioned in the section

  Specific examples of the anthraquinone dye that can be used as a precursor of a dye monomer having an anthraquinone dye skeleton include the following acidic dyes and oil-soluble dyes, but are not limited thereto.

[Anthraquinone acid dyes]
As an anthraquinone acid dye, CI Acid Blue 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 51, 53, 55, 56, 62, 68, 69, 78, 80 81: 1, 11, 124, 127, 127: 1, 140, 150, 175, 215, 230, 277, 344, CI Acid Violet 41, 42, 43, CI Acid Green 25, 27 Or direct violet 17 and the like.

[Anthraquinone oil-soluble dye]
Examples of anthraquinone oil-soluble dyes include CI Solvent Red 172, 222, CI Solvent Violet 60, and the like.

<Triarylmethane dye skeleton>
Examples of the triarylmethane dye skeleton include a diaminotriarylmethane dye skeleton, a triaminotriarylmethane dye skeleton, and a rosic acid dye skeleton having an OH group.
Triaminotriarylmethane-based dye skeletons are preferable in that they are excellent in color tone and more excellent in fastness to sunlight than others. Among them, a diphenylnaphthylmethane dye skeleton that is a basic dye is particularly preferable.
The triarylmethane dye skeleton has a spectral characteristic having a high transmittance in the wavelength range of 400 to 430 nm. By using it as the pigment monomer (A) of the present invention, not only the spectral characteristic but also the resistance can be obtained. Can also be an excellent colorant.

  Among the triarylmethane dye skeletons, the triarylmethane dye skeletons represented by the general formulas (4-1) and (4-2) are preferable because they are excellent in lightness and resistance.

In general formulas (4-1) and (4-2),
R ₂₁₁ , R ₂₁₂ , R ₂₁₃ , R ₂₁₄ , R ₂₃ , and R ₂₄ each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituent. Represents a good phenyl group, or adjacent Rs are bonded to form a ring.
R ₂₂ , R ₂₅ , and R ₂₆ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted group having 2 to 6 carbon atoms. It represents an alkenyl group, an optionally substituted phenyl group, an optionally substituted amino group, or a fluorine atom.
Y ⁻ represents an inorganic or organic anion.
Here, any one of R _{211 to} R ₂₁₄ and R _{22 to} R ₂₆ is a bond with X.

In formulas (4-1) and (4-2), R _{211 to} R ₂₁₄ are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent. An alkyl group having 2 to 5 carbon atoms which may have a substituent is more preferable. R ₂₃ and R ₂₄ are each independently preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, and both R ₂₃ and R ₂₄ are more preferably a hydrogen atom. . R ₂₅ is preferably an amino group which may have a substituent, and R ₂₂ and R ₂₆ are preferably hydrogen atoms.

The bond to X is preferably any one of R ₂₂ , R ₂₅ and R ₂₆ , more preferably R ₂₅ .

  Examples of the “substituent” that the alkyl group, phenyl group, and alkenyl group in the general formulas (4-1) and (4-2) can have include the “substituent groups” mentioned in the section of the xanthene dye skeleton. Same as “A”.

  Specific examples of the triarylmethane dye that can be used as a precursor of a dye monomer having a triarylmethane dye skeleton include the following acidic dyes and basic dyes, but are not limited thereto. It doesn't let you.

[Triarylmethane acid dyes]
Examples of triarylmethane acid dyes include CI Acid Blue 1, 3, 5, 7, 9, 11, 15, 17, 19, 22, 24, 38, 48, 75, 83, 90, 91, 93. 93: 1, 100, 103, 104, 109, 110, 119, 147, 269, 123, 213, CI Direct Blue 41, CI Acid Violet 17, 19, 21, 23, 25, 38 49, 72, direct blue 41, and the like.

[Triarylmethane basic dye]
Examples of the triarylmethane basic dye 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.
Among them, C.I. I. Basic Blue 7, Green 4, Green 1, and Violet 3 are preferably used.

[Counter anion Y ⁻ ]
Y ^- represents an anion. Y ⁻ is the same as the anion mentioned in the section of the xanthene dye.

(Method for producing dye monomer (A))
As a method for synthesizing the dye monomer (A) of the present invention, a polymerizable moiety is introduced into a basic skeleton of an organic dye having a functional group by a general organic synthesis technique, or a polymerizable moiety is added to an organic dye synthesis raw material. Can be obtained by synthesizing a dye.
For example, the dye monomer (A) can be produced by reacting an organic dye having a hydroxyl group with a carboxylic acid chloride having a polymerizable group to form an ester bond therebetween.
Alternatively, a dye monomer (A) can be produced by reacting an organic dye having a carboxyl group with a polymerizable compound having an epoxy group or a polymerizable compound having a hydroxyl group. Even if this method is used, there is no limitation as long as the dye monomer (A) of the present invention is obtained.

  Examples of organic dyes that can be used as raw materials include acid dyes, oil-soluble dyes, basic dyes, etc., and the obtained dye monomers have a structure represented by the general formula (1) As long as it is synthesized using any organic dye, compound or the like, there is no limitation.

(Salt-forming compound and derivative of dye monomer (A))
The dye monomer (A) has good spectral characteristics and excellent color developability, but has a problem in light resistance and heat resistance, and is used for an image display device using a color filter that requires high reliability. In some cases, the characteristics may not be sufficient.
Therefore, in order to improve these disadvantages, in the case of the basic dye form, it is preferable from the viewpoint of resistance to form a salt using an organic acid, perchloric acid or a metal salt thereof.
In the case of acid dyes and direct dyes, quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., and a resin component having these functional groups can be used for salt formation. It is preferable in terms of resistance to use it as a salt-forming compound or to use it as a sulfonic acid amide compound after sulfonamidation.

  Among these, salt forming compounds of basic dyes are preferable because they are resistant and have excellent compatibility with pigments. Furthermore, basic dyes and organic sulfonic acids, organic sulfuric acid, fluorine, which are counter components that function as counter ions, are preferred. It is possible to use a salt-forming compound obtained by salting a group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, or an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group. It is more preferable.

<< 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. However, the case where it is a pigment monomer (A) is excluded.

  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 preferred triarylmethane-based basic dyes include, but are not limited to, compounds represented by the following general formula (51).

In General Formula (51), R1A to R1F each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.
R2A and R3A each independently represents a hydrogen atom, a methyl group, or an ethyl group.
Y ₁ ^- is an organic or inorganic anion capable of salt exchange with a counter compound.

  Examples of the alkyl group in R1A to R1F and R include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms, or one or more ester bonds (- And a linear, branched, monocyclic or condensed polycyclic alkyl group containing (COO-) and / or an ether bond (-O-). Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert- A pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like can be mentioned. It is not something.

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 containing one or more ether bonds include —CH ₂ —O—CH ₃ , —CH ₂ —CH ₂ —O—. CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1 to 8), _{- (CH 2 -CH 2 -CH 2} -O) m -CH 3 ( here m is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 -CH 3 -, - CH _2- CH- (OCH ₃ ) _{2 and the} like can be mentioned, but are not limited thereto.

  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 alkenyl group in R1A to R1F and 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 vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopenta Although a dienyl group etc. can be mentioned, it is not limited to these.

  The aryl group in R1A to R1F is a monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a p-biphenyl group, m- Biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1-pyrenyl group, 2- Although a pyrenyl group, 3-perylenyl group, etc. can be mentioned, it is not limited to these.

  These alkyl groups, alkenyl groups in R1A to R1F and R, and aryl groups in R1A to R1F may have a substituent. Examples of such a substituent include an alkyl group, an alkenyl group, and an aryl group, and these are as defined above.

  R2A and R3A each independently represents a hydrogen atom, a methyl group, or an ethyl group. Preferably, it is a hydrogen atom or a methyl group.

  The position of the cation of the triarylmethane dye may be anywhere as long as a stable resonance structure can be obtained, and may be any nitrogen portion of the amine portion or the central carbon portion of the triarylmethane.

Y ₁ ^- is an organic or inorganic anion capable of salt exchange with the counter compound in the present invention.
Usually, it is preferably a halogen, such as a chloride ion.

  For example, the triarylmethane dye represented by the general formula (52) can be obtained by salt exchange between a corresponding triarylmethane basic dye and a specific sodium sulfate, potassium salt, ammonium salt or the like.

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 lightness, I. Basic Blue 7 is preferably used.

[Counter compound]
In the present invention, the counter compound is an inorganic or organic anionic compound, and any compound having an anion capable of salt formation with a triarylmethane-based basic dye can be used.

Typical anions include triflate ions (CF ₃ SO ₃ ⁻ ), benzoate ions (C ₆ H ₅ COO ⁻ ), oxalate ions (C ₂ O ₄ ²⁻ ), perhalogenate ions (ClO ₄ ⁻ , FO ₄ ⁻ , BrO ₄ ⁻ , IO ₄ ⁻ etc.), thiocyanate ion (SCN ⁻ etc.), sulfate ion (SO ₄ ²⁻ , HSO ₄ ⁻ etc.), heteropolyacid, organic carboxylate ion, organic sulfonate ion (eg C1-C20 alkyl sulfonate, benzene sulfonate, etc.), fatty acid ion (C1-C20 aliphatic carboxylate, etc.), sulfonic acid group-containing nitrogen anion, fluorine group-containing boron anion, fluorine group-containing phosphorus anion, cyano A group-containing nitrogen anion, an anion having a conjugate base of an organic acid having a halogenated hydrocarbon group, or Such as sexual dyes and the like, it can be preferably used those anions.

Alternatively, resins having these anionic groups in the side chain can be used, and among these resins, resins having an anion moiety of —SO ₃ ^— or —COO ^— are preferable.

  As the counter compound having these, the anionic compounds described in the counter anion that the dye monomer (A) can have can also be used.

Among these anions, from the viewpoint of heat resistance, sulfate ions, organic sulfonate ions, sulfonate group-containing nitrogen anions, or fluorine group-containing boron anions are preferable, and a counter compound having such anions is preferably used.
More preferred is a sulfate ion or an anion having a fluorine group-containing boron anion.

As the sulfate ion, the sulfate represented by the general formula (11) or the general formula (12) or a metal salt thereof is more preferable.
As the fluorine group-containing boron anion, a compound having an anion represented by the general formula (31) is preferable. More preferably, at least one of R ^{12 to} R ^{15 in} the general formula (31) is represented by the general formula (32). It is a compound which is a structure represented.

Moreover, the counter compound as an anion component which can be preferably used is an anionic compound having a molecular weight in the range of 200 to 3500, or a resin having an anionic group in the side chain. As an anionic compound whose molecular weight is in the range of 200-3500,
Specifically, organic acids such as heteropoly acids, 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, Or it has the form of an acid dye. Alternatively, a metal salt thereof may be used.

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 may not be possible.
Furthermore, modification with a resin having an acid group is also 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.

  The counter compound preferably has a form of an organic acid such as organic sulfonic acid or organic carboxylic acid, an organic sulfuric acid such as aliphatic sulfuric acid or aromatic sulfuric acid, a fluorine group-containing boron anion compound or an acidic dye. Among them, organic sulfonic acid, aliphatic sulfuric acid or aromatic sulfuric acid or acidic dye form is preferable, organic sulfonic acid or metal salt thereof, sulfate ester or metal salt thereof (such as aliphatic sulfuric acid or aromatic sulfuric acid), or fluorine group-containing A boron anion compound is more preferred.

(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 or organic sulfuric acid)
Examples of organic acids include organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, and organic sulfuric acids such as aliphatic sulfuric acid and aromatic sulfuric acid. Can be mentioned. Moreover, these metal salts or ammonium salt etc. may be sufficient.

  Among these organic acids or organic sulfuric acids, from the viewpoints of hue, heat resistance and solvent resistance, 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. Is preferred. Among them, the sulfate represented by the following general formula (11) or the general formula (12) or a metal salt thereof is preferable, and aliphatic sulfuric acid or aromatic sulfuric acid, that is, aliphatic sulfate or aromatic sulfate is color reproduction. It is preferable because of its excellent properties. Moreover, the monomer which has a sulfuric acid group represented by 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 or organic sulfuric 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.

"Sulfuric acid ester represented by general formula (11) or general formula (12) or a metal salt thereof"

[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.

[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-1,2,4 -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-naphth Rentrisulfonic 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 Risulfonic 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 trisulfonic 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 3 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-naphth Rentrisulfonic 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 (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 sulfate 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.

[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. ]

[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 In general formula (21), specific examples of the oxyalkylene group which may have a substituent of R ² include oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group, oxy A tetramethylene group, an oxyhexamethylene group, an oxyoctamethylene group, etc .; 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, or para-cumyl phenyl group or the like; in the general formula (21), specific examples of the monovalent alkyl group having 1 to 30 carbon atoms of R ³ include a methyl group, an ethyl group Propyl group, butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group or a dodecyl group; including without being limited thereto.

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 considered 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, Commercially available products from Daiichi Kogyo Seiyaku Co., Ltd. Aqualon KH-10, KH-1025, or polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate such as KH-05; HS-10, HS-1025, BC Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate such as BC-10, BC-20, etc .; Sanyo Kasei Kogyo Co., Ltd. commercial product, Eleminol RS-3000 polyoxyalkylene sodium sulfate methacrylate; Nippon Emulsifier Co., Ltd. commercial product Antox MS -60 bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate Examples include salts.

  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.

(Fluorine group-containing boron anion compound)
The fluorine group-containing boron anion compound of the present invention preferably has an anion represented by the following general formula (31).

[In the general formula (31), R ^{12 to} R ¹⁵ are each independently an alkyl group optionally substituted with a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom, or an aryl group optionally substituted with a fluorine atom. And at least one of R ^{12 to} R ¹⁵ represents an alkyl group optionally substituted with a fluorine atom, a fluorine atom, or an aryl group optionally substituted with a fluorine atom.
However, it excludes when R < ¹² > -R < ¹⁵ > is all fluorine atoms. ]

In the general formula (31), examples of the alkyl group represented by R ^{12 to} R ¹⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. A pentyl group, a hexyl group, an octyl group, an isooctyl group, a decyl group, a dodecyl group, a pentadecyl group and an octadecyl group, which may be substituted with a fluorine atom. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 18 carbon atoms, and 2 to 12 carbon atoms from the viewpoints of solubility in organic solvents, brightness, heat resistance, and contrast ratio. More preferably.

In the general formula (31), the aryl group represented by R ^{12 to} R ¹⁵ has a group containing a benzene ring, a group containing a condensed ring having aromaticity, two or more benzene rings or aromaticity. A group having a structure in which fused rings are directly bonded, a group in which two or more benzene rings or a condensed ring having aromaticity are bonded via a group such as vinylene are included. The aryl group preferably has 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms. Examples of the aryl group substituted with a fluorine atom include a phenyl group which may have a fluorine group, a 1-naphthyl group which may have a fluorine group, and a fluorine group which may have 2 -A naphthyl group is mentioned. From the viewpoint of heat resistance, lightness, and contrast ratio, it is preferable that a fluorine atom has a substituent.

Specific examples of the fluorine group-containing boron anion include (CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , and (CF ₃ ) as the fluorine group-containing boron anion represented by the general formula (31). ^{_{2 BF 2 -, (CF 3}} ) BF 3 -, (C 2 F 5) 4 B -, (C 2 F 5) 3 BF -, (C 2 F 5) BF 3 -, (C 2 F 5) 2 ^{_{BF 2 -, (CF 3)}} (C 2 F 5) 2 BF -, (C 6 F 5) 4 B -, [(CF 3) 2 C 6 H 3] 4 B -, (CF 3 C 6 H 4 ^{_{) 4 B -, (C 6}} F 5) 2 BF 2 -, (C 6 F 5) BF 3 -, (C 6 H 3 F 2) 4 B -, B (CN) 4 -, B (CN) F ^{_{3 -, B (CN) 2}} F 2 -, B (CN) 3 F -, (CF 3) 3 B (CN) -, (CF 3) ^{_{2 B (CN) 2 -,}} (C 2 F 5) 3 B (CN) -, (C 2 F 5) 2 B (CN) 2 -, (n-C 3 F 7) 3 B (CN) -, ^{_{(n-C 4 F 9)}} 3 B (CN) -, (n-C 4 F 9) 2 B (CN) 2 -, (n-C 6 F 3) 3 B (CN) -, (CHF 2) ^{_{3 B (CN) -, (}} CHF 2) 2 B (CN) 2 -, (CH 2 CF 3) 3 B (CN) -, (CH 2 CF 3) 2 B (CN) 2 -, (CH 2 C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B (CN) ₂ ⁻ , (n—C _{3 F 7 CH 2) 2 B (} CN) 2 -, (C 6 H 5) 3 B (CN) - , and the like.
Among these, B (CN) ₃ F ⁻ , (CF ₃ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , and [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ are preferable.
The counter of the fluorine group-containing boron anion compound is Na ⁺ or K ^+, tetrabutylammonium or trimethylammonium.

In general formula (31), at least one of R ^{12 to} R ¹⁵ is preferably a structure represented by general formula (32).

[In General Formula (32), R ^{16 to} R ²⁰ each independently represent a hydrogen atom or a fluorine atom. However, when R ¹⁶ to R ²⁰ are all hydrogen atoms is excluded. ]

Examples of the substituent represented by the general formula (32) include a pentafluorophenyl group (C ₆ F ₅ ), a trifluorophenyl group (C ₆ H ₂ F ₃ ), a tetrafluorophenyl group (C ₆ HF ₄ ), Trifluoromethylphenyl group (CF ₃ C ₆ H ₄ ), bis (trifluoromethyl) phenyl group ((CF ₃ ) ₂ C ₆ H ₃ ), pentafluoroethylphenyl group (CF ₂ CF ₃ C ₆ H ₄ ), Bis (pentafluoroethyl) phenyl group ((CF ₂ CF ₃ ) ₂ C ₆ H ₃ ), fluoro-trifluoromethylphenyl group (CF ₃ C ₆ H ₃ F), fluoro-bis (trifluoromethyl) phenyl group ( _{(CF 3) 2 C 6 H} 2 F), fluoro - pentafluoroethyl phenyl group _{(CF 3 CF 2 C 6 H} 3 F), fluoro - bis (Bae Such as motor-fluoroethyl) phenyl group _{((CF 3 CF 2) 2} C 6 H 2 F) can be mentioned.
Of these, [B (C ₆ F ₅ ) ₄ ] ^— _, [(C ₆ H ₅ ) B (C ₆ F ₅ ) ₃ ] ^— _, [(C ₆ H ₅ ) from the viewpoint of brightness, heat resistance, and contrast ratio. ) ₂ B (C ₆ F ₅ ) ₂ ] ^— _, [(C ₆ H ₅ ) ₃ B (C ₆ F ₅ )] ^— _, [(C ₆ H ₅ ) B (C ₆ H ₃ (CF ₃ ) ₂ ) ₃ ³ ] ^{-and the} like. Of these, [B (C ₆ F ₅ ) ₄ ] ^— is preferable.

(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. By modifying with a resin having an anionic group in the side chain, heat resistance and light resistance can be imparted and good solubility can be obtained.

  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.

[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, 1 to 12 C atoms. A linear or branched alkyl group, a mono- or polyunsaturated alkenyl group having 2 to 12 linear or branched C atoms (where the latter two groups are 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 saturated or unsaturated A straight or branched hydrocarbon having 1 to 12 C atoms; X is a single bond, n = 1 to 4 — (CH ₂ ) n—, phenylene, preferably 1,4-phenylene , —CH ₂ —O-phenylene (preferably 1, 4), —CH ₂ —O—CH ₂ —C H (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 . ]

Particularly advantageous among the monomers having sulfonic acid groups are the monomers of formula (IVa), (IVb) and / or (IVc).
_{(IVa) H 2 C = CH} -X-SO 3 H
_{(IVb) H 2 C = C} (CH 3) -X-SO 3 H
(IVc) HO ₃ S—X— (R ₁₀ ) C═C (R ₁₁ ) —X—SO ₃ H
[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.

  Moreover, it is preferable from the surface of brightness and tolerance to use the ethylenically unsaturated monomer (a-1) shown by the above-mentioned general formula (21) as the monomer having a sulfate group.

"Other ethylenically unsaturated monomers"
Other ethylenically unsaturated monomers include monomers containing sulfonic acid groups and / or carboxyl groups, or ethylenically unsaturated monomers (a-1) represented by general formula (21) and radical polymerization. If it is possible, it will not specifically limit, According to a use, it can select suitably. 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 polydimethyl Siloxanes (silicone macromers); (meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (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. (Meth) acrylates having the following aromatic ring;

  (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 ( N-substituted (meth) acrylamides such as meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine; N, N-dimethylaminoethyl (meth) acrylate, or N, N- Amino group-containing (meth) acrylates such as diethylaminoethyl (meth) acrylate; nitriles such as (meth) acrylonitrile; 1,2,2,6,6, -pentamethylpiperidyl (meth) acrylate and 2,2,6 , 6, Hines such as tetramethylpiperidyl (meth) acrylate Containing antioxidant unit having Doamin skeleton (meth) acrylates; or mixtures thereof.

  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) WO 96/030421 (reference 6) WO 97/018247 (reference 7) JP-A-9-208616 No. 8 (Reference 8) Japanese Patent Laid-Open No. 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.

  A monomer containing a sulfonic acid group and / or a carboxyl group, or an ethylenically unsaturated monomer (a-1) represented by the general formula (21), which is suitable for the present invention, is an all ethylenically unsaturated monomer. (A) 10% to 95% by weight based on the weight is preferable, and more preferably 20% to 60% by weight.

  When the weight of the monomer containing a sulfonic acid group and / or a carboxyl group or the ethylenically unsaturated monomer (a-1) represented by the general formula (21) is less than 10% by weight, a salt-forming reaction is caused. The proportion of cationic dyes that occur is reduced. 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 it exceeds 95% by weight, an ethylenically unsaturated monomer comprising a monomer containing a sulfonic acid group and / or a carboxyl group, or an ethylenically unsaturated monomer (a-1) represented by the general formula (21) Since the amount of the cationic dye salted into the resin obtained by radical polymerization of the body (a) becomes too large, the heat resistance deteriorates, which is not preferable.

  A monomer containing a sulfonic acid group and / or a carboxyl group used in the present invention, or an ethylenically unsaturated monomer including the ethylenically unsaturated monomer (a-1) represented by the general formula (21) ( The molecular weight of the resin obtained by radical polymerization of a) is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000. 3,000 to 15,000 is more preferable.

  Moreover, the ethylenically unsaturated monomer containing the monomer containing a sulfonic acid group and / or carboxyl group suitable for this invention, or the ethylenically unsaturated monomer (a-1) shown by General formula (21) As the resin obtained by radical polymerization of (a), a mixed solution with an organic solvent 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 apparatus: HLC-8120 GPC column manufactured by Tosoh Corporation Co., Ltd .: 3-connected flow rate of TSK Guardcolumn Super H-HT / SK-GEL / Super HM-M manufactured by Tosoh Corporation: 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.

《Phthalocyanine dye》
The composition of the present invention preferably further contains a phthalocyanine dye.
By further containing a phthalocyanine dye, it is possible to obtain a colored composition having more excellent resistance.
Examples of the phthalocyanine dyes include acid dyes, basic dyes, direct dyes, ingredient dyes, mordant dyes, reactive dyes, organic solvent-soluble dyes, disperse dyes, and vat dyes. Specific examples of the phthalocyanine dye are listed below, but are not limited thereto.
However, the case where it is a pigment monomer (A) is excluded.

Examples of the phthalocyanine dye include C.I. I. Acid Blue 185, 197, 224, 228, 242, 243, 249, 275, 279, 283, 310, 357, C.I. I. Basic Blue 33, 33: 1, 63, 82, 126, 138, 140, 157, 160, 161, 164, C.I. Direct Blue 86, 87, 189, 199, 262, 264, 276, 282, 314, C.I. I. Disperse Blue 329, C.I. I. Ingle Blue 1, 2, 2, 2: 1, 2: 2, 3, 4, 5, 11, 12, 12, 15, 17, 17: 1, 19, C . I. Modern Blue 58, 77, C.I. I. Reactive Blue 3, 7, 11, 11, 17, 18, 21, 21, 23, 25, 35, 38, 57, 58, 71, 72, the same 75, 77, 80, 85, 88, 91, 92, 95, 105, 106, 116, 118, 118: 1, 123, 124, 136, 138, 140, 151, 159, 169, 190, 197, 207, 215, 231, C.I. I. Solvent Blue 24, 25, 38, 44, 46, 48, 51, 52, 55, 64, 67, 70, 75, 89, 117, 129 131, 142, C.I. I. Bat Blue 29, 57, etc.
Among them, C.I. I. Direct Blue 86, 87, 189, 199, C.I. It is preferable to use I. Solvent Blue 38 and 70.

  From the viewpoint of obtaining sufficient color reproducibility and resistance, the preferable concentration of the phthalocyanine dye is 0.001% by weight or more, more preferably 0, based on the total nonvolatile components of the colored composition of the present invention (100% by weight). 0.005% by weight or more, and most preferably 0.01% by weight. Further, since the stability of the coloring composition is improved, the preferred concentration of the phthalocyanine dye component is 10% by weight or less, more preferably 5% by weight or less, and most preferably 1% by weight or less.

《Other colorants》
The coloring composition for a color filter of the present invention can further contain other coloring agent in addition to the pigment monomer (A), the salt-forming compound (B), and the phthalocyanine dye. 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 the 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, 58, JP 2008-19383 Examples thereof include zinc phthalocyanine pigments described in JP-A-2007-320986, JP-A-2004-70342, and the like. Can be mentioned. 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 with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and 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.

<Binder resin>
The binder resin is a colorant, in particular, one that disperses the dye monomer (A) and the salt-forming compound (B) of the present invention, or the dye monomer (A) and salt-forming compound (B) of the present invention. Etc., such as thermoplastic resins and thermosetting resins.

  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 using a binder resin as a coloring composition for a color filter, from the viewpoints of dispersibility, penetrability, developability, and heat resistance of the dye monomer (A) and the salt-forming compound (B) of the present invention. The balance between the colorant-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. It is preferable to use this resin. 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 wt% 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.

<Photocationic polymerization initiator (C)>
The cationic photopolymerization initiator (C) generates a strong acid such as tetrafluoroboric acid or hexafluorophosphoric acid by UV irradiation or heating, and this 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 a cationic photopolymerization initiator, 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 thianthrenium, and the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or [BX ₄ ] ⁻ (where X is a hydrogen atom of the phenyl group) An aromatic sulfonium salt (C1), an aromatic iodonium salt (C2), an aromatic diazonium salt, an aromatic, each having two or more functional groups substituted by a fluorine atom or a trifluoromethyl group. Ammonium salt, thioxanthonium salt, or (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene Zen] - 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, an aromatic sulfonium salt (C1) or an aromatic iodonium salt (C2) is preferable for improving the remaining film ratio and adhesion, and more preferably an aromatic sulfonium salt from the viewpoint of improving the remaining film ratio. (C1).

  Examples of the aromatic sulfonium salt (C1) 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 (C2) 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-cyclopentadien-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 or the like can be used.

  As a photocationic polymerization initiator (C), for example, CPI-100P, CPI-200K, CPI-101A (manufactured by San Apro Co., Ltd.), Cyracure photocuring initiator UVI-6990, Cyracure 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, or Irgacure 250 made by BASF, which is an aromatic iodonium salt, is an aromatic sulfonium salt (C1). WPI-113, WPI-116, WPI-169, and WPI-170 manufactured by Kojun Pharmaceutical Co., Ltd. are preferable.

<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 trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate and the like monohydroxy oligoacrylates or monohydroxy oligomethacrylates 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, Organic azide compounds described in Japanese Patent Publication No. 47-1604 and diazonium compound publications described in USP 3,567,453, USP 2,848,328, USP 2,852,379, and USP 2,940,553, 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 titanocenes described in Japanese Patent Publication No. Hokukai, "COORDINATION CHEMISTRY REVIEW", Volume 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>
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.

  Moreover, since the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for color filter (100% by weight), the brightness and sensitivity are good. More preferred.

<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 contained in the colored photosensitive composition. From 5 to 50% by weight is more preferable.

<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. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. 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>
In the coloring composition for a color filter of the present invention, a coloring agent containing the coloring matter monomer (A) and the salt-forming compound (B) of the present invention is contained in a coloring agent carrier comprising the resin and a solvent as necessary. In addition, it can be produced by finely dispersing together with a dispersing aid such as a pigment derivative using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor.

  In addition, the coloring composition for a color filter of the present invention is obtained by mixing the pigment monomer (A), the salt-forming compound (B) of the present invention, and other colorants separately dispersed in a colorant carrier. It can also be manufactured. Further, when the solubility of the dye monomer (A) and the salt-forming compound (B) of the present invention is high, specifically, the solubility in a solvent to be used is high, so that no dissolution or foreign matter is confirmed by stirring. If it exists, it is not necessary to manufacture by finely dispersing as described above.

[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, 21116 or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000 manufactured by Lubrizol Japan, 000, 13000, 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, manufactured by BASF Japan 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 45 0, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajinomoto Fine Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc. Can be mentioned.

  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. “PGMEA” means propylene glycol monomethyl ether acetate.

  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.

First, the measurement method of the weight average molecular weight (Mw) and acid value of resin is demonstrated.
(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) 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 manufacturing method of the binder resin, the dye monomer, and the salt-forming compound used in Examples and Comparative Examples will be described.

<Method for producing binder resin solution>
(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 pigment monomer>
(Dye monomer (A-1))
[Dye intermediate (a)]
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is prepared by dissolving 5.0 parts of Basic Violet 10 (Tokyo Chemicals: Rodamine B) and 2.0 parts of glycerol monomethacrylate (GLM) in 50 g of dichloromethane. 2.2 parts and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water, dried under reduced pressure, and then purified on a silica gel column to obtain 1.9 parts of a dye intermediate (a). The yield was 29.5%.

[Dye monomer (A-1)]
1 part of the obtained dye intermediate (a) was dissolved in 100 parts of water, 1.4 parts of NaB (C ₆ F ₅ ) ₄ was added thereto, and the mixture was stirred at room temperature for 2 hours. After filtration and washing with water, it was dried at 80 ° C. to obtain 1.7 parts of a dye monomer (A-1). The yield was 85.1%.

(Dye monomer (A-2))
1 part of the dye intermediate (a) is dissolved in 100 parts of water, and 1.4 parts of cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium salt (manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.) is added thereto. Then, stirring was performed at room temperature for 2 hours. After filtration and washing with water, it was dried at 80 ° C. to obtain 1.7 parts of a dye monomer (A-2). The yield was 85.1%.

(Dye monomer (A-3))
1 part of the dye intermediate (a) was dissolved in 100 parts of water, and 1.4 parts of sodium dodecyl sulfate (Tokyo Chemicals) was added thereto, followed by stirring at room temperature for 2 hours. After filtration and washing with water, it was dried at 80 ° C. to obtain 1.7 parts of a dye monomer (A-3). The yield was 85.1%.

(Dye monomer (A-4))
Except for changing glycerin monomethacrylate (GLM) in the production of the dye intermediate (a) to 2-hydroxyethyl acrylate (HEA), the same procedure as for the dye monomer (A-3) was carried out. A monomer (A-4) was obtained. The yield was 89.3%.

(Dye monomer (A-5))
A dye monomer (A-3) was prepared in the same manner as the dye monomer (A-3) except that glycerin monomethacrylate (GLM) in the production of the dye intermediate (a) was changed to hydroxyethyl methacrylate (HEMA). A-5) was obtained. The yield was 86.3%.

(Dye monomer (A-6))
The dye monomer (A) was prepared in the same manner as the dye monomer (A-1) except that glycerol monomethacrylate (GLM) in the production of the dye intermediate (a) was changed to glycerol dimethacrylate (GMR). -6) was obtained. The yield was 87.8%.

(Dye monomer (A-7))
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. Solvent RED 172 (SR172: Sunbelt: Morolas Magenta36) is dissolved in 5.0 parts and 3-acryloyloxypropanoic acid (1.6 parts) is dissolved in dichloromethane (40 ml) to give 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide. 2.2 parts of hydrochloride and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water and dried under reduced pressure, and then purified on a silica gel column to obtain a dye monomer (A-7). The yield was 46.8%.

(Dye monomer (A-8))

[Compound (1)]
To a 1 L stainless steel reaction vessel equipped with a reflux tube, 2.75 parts of 1-naphthaleneacetic acid (manufactured by Aldrich), 25 parts of dehydrated toluene and 0.03 part of p-toluenesulfonic acid were added under a nitrogen atmosphere. Heated to 70 ° C. After heating, 1.92 parts of hydroxyethyl methacrylate was added and heated to 80 ° C. and stirred for 3 hours. Then, 3.2 parts of compounds (1) were obtained by removing a solvent with an evaporator.

[Compound (2)]
1.3 parts of phosphorus oxychloride was added to a mixture of 3 parts of the obtained compound (1), 2.1 parts of compound (2) and 20 parts of toluene, and the mixture was stirred at 120 ° C. for 2 hours. After allowing to cool to room temperature, 1N aqueous hydrochloric acid solution was added, and the mixture was stirred for 15 minutes and extracted with chloroform. The chloroform layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (chloroform / methanol 15/1 → 7/1), and the solid was purified with hexane. To obtain 2.8 parts of compound (3).

[Dye monomer (A-8)]
1 part of the obtained compound (3) was dissolved in 100 parts of water, and 1.4 parts of NaB (C ₆ F ₅ ) ₄ was added thereto, followed by stirring at room temperature for 2 hours. After filtration and washing with water, it was dried at 80 ° C. to obtain 1.7 parts of a dye monomer (A-8). The yield was 85.1%.

<Method for producing salt-forming compound>
(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 salt-forming compounds (B-1). The yield was 84.8%.

(Salt-forming compound (B-2))
C. I. 12 parts of Basic Blue 7 (Tokyo Chemicals), 7.4 parts of NaBF ₄ , 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 salt-forming compounds (B-2). The yield was 84.8%.

(Salt-forming compound (B-3))
C. I. 12 parts of Basic Blue 7 (Tokyo Chemicals), 7.4 parts of NaB (C ₆ F ₅ ) ₄ , 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-3). The yield was 84.8%.

(Salt-forming compound (B-4))
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 (PGMEA) 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 the 60 degreeC vacuum dryer, and obtained 40.0 parts pigment | dye (salt-forming compound B-4). The yield was 78.7%.

(Salt-forming compound (B-5))
[Compound (4)]
To a mixture of 25 parts of 4-diethylaminobenzoic acid (Tokyo Chemicals) and 90 parts of toluene, 23 parts of thionyl chloride was added and stirred at 80 ° C. for 1 hour, followed by concentration under reduced pressure to obtain acid chloride. In a separate container, 20.4 parts of anhydrous aluminum chloride and 130 parts of 1,2-dichloroethane were added. After cooling in an ice bath, a solution having acid chloride dissolved in 60 parts of 1,2-dichloroethane was added dropwise. After the dropping, the mixture was stirred for 15 minutes, 21 parts of N, N-diethyl-m-toluidine (Tokyo Chemicals) was added dropwise, returned to room temperature, and stirred for 2 hours. Thereafter, the mixture was poured into ice water, adjusted to pH 11 or higher with 4N sodium hydroxide, and extracted with chloroform. This was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (hexane / ethyl acetate = 4/1). The purified product was further dissolved in THF and reprecipitated with hexane. After drying under reduced pressure at 60 ° C., 15.4 parts of compound (4) was obtained. The yield was 35.0%.

[Compound (5)]
10 parts of the obtained compound (4) and 5.0 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 40 parts of toluene, 6.8 parts of phosphorus oxychloride was added and refluxed for 3 hours. I let you. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 13.8 parts of compound (5) was obtained. The yield was 88.8%.

[Salt-forming compound (B-5)]
12 parts of the obtained compound (5), 7.21 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 13.7 parts of salt formation compounds (B-5). The yield was 79.7%.

(Salt-forming compound (B-6))
12 parts of Compound 2 obtained in the production of the salt-forming compound (B-5), 7.4 parts of NaB (C ₆ F ₅ ) ₄ , 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 13.7 parts of salt-forming compound (B-6). The yield was 79.7%.

(Salt-forming compound (B-7))

[Compound (6)]
10.0 parts of N, N-diethyl-m-toluidine (Tokyo Chemicals), 2.5 parts of 37% formaldehyde aqueous solution (Tokyo Chemicals), 7.2 parts of concentrated hydrochloric acid (Kishida Chemicals), 80. 0 parts were mixed, stirred at 80 ° C. for 6 hours, and then allowed to cool to room temperature. Thereafter, 100 parts of chloroform and 100 parts of a 10% NaOH aqueous solution were added, followed by extraction with chloroform. This was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 18.3 parts of compound (6). The yield was 92.4%.

[Compound (7)]
6.4 parts of the obtained compound (6), 3.2 parts of chloranil (Tokyo Chemicals), 2.7 parts of sodium chlorite (Kishida Chemical), 50 parts of isopropyl alcohol (Kishida Chemical), ion exchange 8.0 parts of water was mixed, stirred at 80 ° C. for 15 hours, allowed to cool to room temperature, and inorganic salts were removed by suction filtration. Thereafter, the filtrate was dried, and 100 parts of toluene and 100 parts of a 10% NaOH aqueous solution were added, followed by extraction with toluene. This was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 6.0 parts of compound (7). The yield was 86.4%.

[Compound (8)]
10 parts of the obtained compound (7) and 4.9 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 50 parts of toluene, and 6.6 parts of phosphorus oxychloride was added and refluxed for 3 hours. I let you. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 12.4 parts of compound (8) was obtained. The yield was 80.6%.

[Salt-forming compound (B-7)]
12 parts of Compound (8), 7.4 parts of NaB (C ₆ F ₅ ) ₄ , 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 13.7 parts of salt-forming compounds (B-7). The yield was 79.7%.

(Salt-forming compound (B-8))
12 parts of the compound (8) obtained in the production of the salt-forming compound (B-7), 7.21 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. Stir. 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 13.7 parts of salt-forming compounds (B-8). The yield was 79.7%.

<Method for producing other colorant>
(Colorant (C-1))
C. I. Basic Violet 10 (Tokyo Chemicals: Rodamine B) was dissolved in 100 parts of water, and 1.4 parts of NaB (C ₆ F ₅ ) ₄ was added thereto, followed by stirring at room temperature for 2 hours. After filtration, washing with water and drying at 80 ° C., 1.7 parts of a colorant (C-1) was obtained. The yield was 85.1%.

[Example 1]
(Coloring composition (SR-1))
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
A colored composition (SR-1) was obtained.

Dye monomer (A-1): 0.3 part Salt-forming compound (B-1): 1.4 parts Acrylic resin solution (R-1): 47.0 parts PGMEA: 51.3 parts Propylene glycol monomethyl ether acetate

[Examples 2 to 17, Comparative Examples 1 to 7]
(Coloring composition (SR-2 to 24))
A colored composition (SR-2 to 24) was obtained in the same manner as the colored composition (SR-1) except that the composition and the amount (parts by weight) shown in Table 1 and Table 2 were changed.

<Evaluation of coloring composition>
About the obtained coloring composition (SR-1-24), the heat resistance test was done with the following method. The results are shown in Table 1 and Table 2.

(Evaluation of heat resistance)
A colored composition was applied onto 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 using a microspectrophotometer (“OS
P-SP200 "). Thereafter, the substrate was heated at 230 ° C. for 60 minutes, and again the brightness (
Y2) was measured. 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. In addition, (double-circle) is a very good level, (double-circle) is a favorable level, (circle) is a level which can be used practically, (triangle | delta), and x are levels which are not suitable for practical use.

◎◎ ・ ・ ・ 0.95 or more ◎ ・ ・ ・ 0.90 or more and less than 0.95 ○ ・ ・ ・ 0.85 or more and less than 0.90 △ ... 0.75 or more and less than 0.85 × ・ ・ ・ 0 Less than .75

[Example 18]
(Resist material (CR-1))
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-1).

Dye monomer (A-1): 0.3 parts Salt-forming compound (B-1): 1.4 parts Acrylic resin solution (R-1): 41.0 parts Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.) "Aronix M-402"): 6.0 parts photopolymerization initiator ("Irgacure OXE02" manufactured by BASF Japan): 0.6 parts antioxidant ("Irganox 1010" manufactured by BASF Japan): 0.2 Parts ("Irgaphos 168" manufactured by BASF Japan): 0.6 parts PGMEA: 49.9 parts Propylene glycol monomethyl ether acetate

[Examples 19 to 38, Comparative Examples 8 to 14]
(Resist material (CR-2 to 28))
Resist materials (CR-2 to 28) were obtained in the same manner as the resist material (CR-1) except that the compositions and amounts (parts by weight) shown in Tables 3 and 4 were changed.

<Evaluation of coloring composition>
About the obtained resist material (CR-1 to 28), the heat resistance, lightness, and solvent resistance test were done by the following method. The results are shown in Table 3 and Table 4.

(Evaluation of heat resistance and brightness)
A resist material was applied onto a glass substrate so that y = 0.090 and x = 0.139 with a C light source, and a substrate was manufactured. 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 at this time by Y1 was used as an index of heat resistance. The evaluation criteria are as follows. In addition, (double-circle) is a very good level, (double-circle) is a favorable level, (circle) is a level which can be used practically, (triangle | delta), and x are levels which are not suitable for practical use.

◎◎ ・ ・ ・ 0.95 or more ◎ ・ ・ ・ 0.90 or more and less than 0.95 ○ ・ ・ ・ 0.85 or more and less than 0.90 △ ... 0.75 or more and less than 0.85 × ・ ・ ・ 0 Less than .75

(Evaluation of brightness)
After heating at 230 ° C. for 60 minutes on a glass substrate, a resist material was applied so that the chromaticity in a C light source was y = 0.090 and x = 0.139, and a substrate was produced. The brightness of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
If the chromaticity shifts, create a colored composition in which the ratio of the dye monomer (A) and the salt-forming compound (B) is appropriately changed, measure the chromaticity, and draw a calibration curve to obtain the desired color. The brightness in degrees was calculated.

(Evaluation of solvent resistance)
A resist material was applied on a glass substrate so that y = 0.090 with a C light source, and the substrate was heated at 230 ° C. for 20 minutes. Then, chromaticity 1 with C light source (L * (1), a * (1), b * (
1)) was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Thereafter, the substrate was immersed in N-methylpyrrolidone for 15 minutes, and the chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured again.

Using the measured chromaticity value, the color difference ΔEab * was calculated by the following formula.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
Based on the color difference ΔEab *, the solvent resistance of the coating film was evaluated according to the following criteria.
In addition, (circle) is a favorable level, (triangle | delta) is a practical use level, and x is a level unsuitable for practical use.

○: ΔEab * is less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

Abbreviations in Tables 3 to 5 are described below.
Photopolymerizable monomer Aronix M-402; Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator Irgacure OXE02;
("Irgacure OXE02" manufactured by BASF Japan)
・ Photo cationic polymerization initiator
Irgacure 290;
("Irgacure 290" manufactured by BASF Japan:
The antioxidant Irganox 1010;
("Irganox 1010" manufactured by BASF Japan)
Irgaphos 168;
("Irgaphos 168" manufactured by BASF Japan)

From the results shown in Table 1, the colorant is a salt-forming compound (B) comprising a dye monomer (A) represented by the general formula (1), a triarylmethane basic dye and a counter compound having an anionic group. It was confirmed that the coloring composition was excellent in heat resistance, lightness, and solvent resistance.
In addition, the coloring composition 14 of the comparative example 14 was not able to match | combine a hue.

  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 (11)

A color filter coloring composition comprising a colorant, a binder resin, and a solvent, wherein the colorant comprises a dye monomer (A) represented by the following general formula (1), and a triarylmethane series A salt-forming compound (B) of a basic dye and a counter compound having an anionic group (except in the case of the dye monomer (A)), and the content of the dye monomer (A) is The coloring composition for a color filter, characterized by being 1 to 80 parts by weight per 100 parts by weight of the salt-forming compound (B) .

[In General Formula (1), Q represents an organic dye skeleton.
X is a direct bond, —R ₂ —, —NH—R ₃ —, —O—R ₃ —, —CO—R ₃ —, —COO—R.
₃ — or —O—CO—R ₃ — is represented.
R ₁ represents a hydrogen atom or a methyl group.
R ₂ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted ester bond (—C
At least one bond selected from OO-) or ether bond (-O-).
An alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, —R ₄ —O—R ₅ —, —R ₄ —CO—R ₅ —, —R ₄ —COO—R ₅ , -R ₄ -O-
CO—R ₅ —, —R ₄ —O—CONH—R ₅ —, or —R ₄ —O—CO—R ₆ —CO—R ₅ —
Represents.
R ₃ represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, —R ₄ —O—R ₅ —, —R ₄ —CO—R ₅ —, —R _4- O
—CO—R ₅ —, —R ₄ —O—CONH—R ₅ —, or —R ₄ —O—CO—R ₆ —CO—R ₅
-Represents.
R ₄ and R ₆ each independently represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, or a substituted or unsubstituted arylene group.
R ₅ represents a substituted or unsubstituted alkylene group, or —O—CH ₂ —CHOH—CH ₂ —. ] The organic dye skeleton Q in the general formula (1) is a xanthene dye skeleton represented by the following general formula (2), an anthraquinone dye skeleton represented by the following general formula (3-1), and the following general formula (3-2). An anthraquinone dye skeleton represented by formula (3-3), an anthraquinone dye skeleton represented by formula (3-3), a triarylmethane dye skeleton represented by formula (4-1) below, and a formula (4-2) The coloring composition for a color filter according to claim 1, which is at least one organic dye skeleton selected from the group consisting of triarylmethane dye skeletons represented by

[In general formula (2),
R _{31 to} R ₃₄ each independently represents a hydrogen atom or a monovalent substituent, and R ₃₁ and R ₃₂ , and R ₃₃ and R ₃₄ may form a ring structure.
R ₃₅ each independently represents a monovalent substituent, and m represents an integer of 0 to 5.
Y ⁻ represents an inorganic or organic anion.
Here, any one of R _{31 to} R ₃₅ is a bond with X. ]
[In the general formulas (3-1), (3-2), and (3-3),
R ₄₁ is a hydrogen atom, -ROH (R is an alkylene group having 1 to 5 carbon atoms), - RCOOH (R is an alkylene group having 1 to 5 carbon atoms) represents a phenyl group which may have a or substituent.
R _{42 to} R ₄₈ are each independently a hydrogen atom, a hydroxyl group, —NHR ₄₉ (R ₄₉ and R ₄₁ have the same meaning), an SO ₃ M group (M is a hydrogen ion or a metal ion), a halogen atom, —COR. '(R' represents an alkyl group having 1 to 3 carbon atoms).
Here, any one of R _{41 to} R ₄₈ is a bond with X. ]
[In the general formulas (4-1) and (4-2),
R ₂₁₁ , R ₂₁₂ , R ₂₁₃ , R ₂₁₄ , R ₂₃ , and R ₂₄ each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or a substituent. Represents a good phenyl group, or adjacent Rs are bonded to form a ring.
R ₂₂ , R ₂₅ , and R ₂₆ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted group having 2 to 6 carbon atoms. It represents an alkenyl group, an optionally substituted phenyl group, an optionally substituted amino group, or a fluorine atom.
Y ⁻ represents an inorganic or organic anion.
Here, any one of R _{211 to} R ₂₁₄ and R _{22 to} R ₂₆ is a bond with X. ]   The counter compound of the salt-forming compound (B) is an organic sulfonic acid or a metal salt thereof, a sulfate ester or a metal salt thereof, a resin having an anionic group in a side chain, or a fluorine group-containing boron anion compound. The coloring composition for a color filter according to claim 1 or 2. The colored composition for a color filter according to claim 3, wherein the sulfate ester or a metal salt thereof is represented by the following general formula (11).

[In general formula (11), R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group,
M ⁺ each independently represents a hydrogen ion or a metal ion.
n represents an integer of 1 to 4. ] The colored composition for a color filter according to claim 3, wherein the sulfate ester or a metal salt thereof is an ethylenically unsaturated monomer (a-1) represented by the general 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),
Y ⁺ represents an inorganic or organic cation. ]

[In general formula (22),
R ⁴ represents an alkylene group which may have a substituent, and is an integer of n = 1 to 20. ] The coloring composition for a color filter according to claim 3, wherein the fluorine-containing boron anion compound has an anion represented by the following general formula (31).

[In general formula (31),
R ^{12 to} R ¹⁵ each independently represents an alkyl group which may be substituted with a fluorine atom, a cyano group, a hydrogen atom, a fluorine atom or an aryl group which may be substituted with a fluorine atom;
At least one of R ^{12 to} R ^{15 represents} an alkyl group which may be substituted with a fluorine atom, a fluorine atom, or an aryl group which may be substituted with a fluorine atom.
However, it excludes when R < ¹² > -R < ¹⁵ > is all fluorine atoms. ] At least one of R ¹² to R ¹⁵ are, according to claim 6 for a color filter colored composition, wherein it is a structure represented by the general formula (32).

[In general formula (32),
R ^{16 to} R ²⁰ each independently represent a hydrogen atom or a fluorine atom.
However, when R ¹⁶ to R ²⁰ are all hydrogen atoms is excluded. ]   Furthermore, the coloring composition for color filters of any one of Claims 1-7 containing a phthalocyanine dye (however, except the case where it is a pigment monomer (A)).   Furthermore, the coloring composition for color filters of any one of Claims 1-8 containing a photopolymerizable monomer and / or a photoinitiator.   Furthermore, antioxidant is included, The coloring composition for color filters of any one of Claims 1-9 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 10 on a substrate.