JP6349629B2 - 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 light 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, a solution has been studied as in Patent Document 3, but there is a disadvantage that the color filter becomes a thick film and becomes incompatible as a member. Further, as described in Patent Document 4, for example, 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 JP 2000-162429 A JP 2008-304766 A

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

  As a result of intensive studies to solve the above-mentioned problems in consideration of the above problems, the inventors of the present invention can achieve high brightness by including a dye monomer having a specific structure. As a result, the inventors have found that excellent performance can be achieved with respect to the performance of the present invention.

That is, the present invention is a color filter coloring composition containing a colorant, a resin, and a solvent, wherein the colorant is a dye monomer (A) represented by the following general formula (1): And a pigment (B), wherein the pigment (B) contains a phthalocyanine skeleton.
General formula (1)
[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 skeleton represented by the following general formula (2), an anthraquinone skeleton represented by the following general formula (3-1), and the following general formula ( 3-2), an anthraquinone skeleton represented by the following general formula (3-3), a triphenylmethane skeleton represented by the following general formula (4-1), and a general formula (4- The coloring composition for color filters, which is at least one organic dye skeleton selected from the group consisting of the triphenylmethane skeleton represented by 2).

General formula (2)

[In General Formula (2), R _{31 to} R ₃₄ each independently represents a hydrogen atom or a monovalent substituent, R ₃₁ and R ₃₂ , and R ₃₃ and R ₃₄ form a ring structure. Also good. 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. ]

General formula (3-1) General formula (3-2)

[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 each independently represent a hydrogen atom, a hydroxyl group, -NHR ₄₉ (R ₄₉ and R ₄₁ has the same meaning), SO ₃ M group, a halogen atom, -COR '(R' is 1-3 carbon atoms Represents an alkyl group of
Here, any one of R _{41 to} R ₄₈ is a bond with X. ]

General formula (4-1) General formula (4-2)

[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. An alkenyl group, an optionally substituted phenyl group, or a fluorine atom is represented. 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 pigment (B) is C.I. I. It is related with the blue coloring composition for the said color filter characterized by being pigment blue 15: 6.

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

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

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

  The coloring composition for a color filter of the present invention includes a dye monomer having a specific structure, 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).

<Dye monomer (A)>
The coloring composition for color filters of this invention contains the pigment | dye monomer (A) described by General formula (1) as a coloring agent. It is also preferable to use an organic pigment (B) in combination. The dye monomer (A) represented by the general formula (1) is improved in solubility in an organic solvent than a normal dye due to the effect of adding a functional group at the end, and has fastness such as heat resistance. Since it contributes to improvement, it is suitable as a coloring composition for a color filter.

General formula (1)

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.) Ed; Kodansha, 1986).

Q is preferably an organic dye selected from the group consisting of xanthene series, anthraquinone series, and triarylmethane series.
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 the xanthene-based, anthraquinone-based, and triarylmethane-based organic dyes, Q is a xanthene-based dye represented by the general formula (2), an anthraquinone-based dye represented by the general formula (3), and a general formula (4 ) Is preferably at least one selected from the group consisting of triarylmethane dyes because the transparency and contrast ratio can be excellent.

(Xanthene dyes)
Xanthene dyes are dyes containing a xanthene ring, and are broadly classified into acidic forms containing hydroxyl groups (fluorescein), basic forms containing amino groups (rhodamines), and mixed systems (rhodols). The Most of them belong to basic dyes or acid dyes and have a remarkably clear color tone. Of these, rhodamine dyes are preferred in terms of color tone.

  Among the xanthene dyes, the xanthene dyes represented by the general formula (2) are preferable because they are excellent in lightness and resistance.

General formula (2)

In the 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. good. 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 substituents that can be taken by R _{31 to} R ₃₄ and R ₃₅ in the general formula (2) are shown in 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 above functional groups, those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups. 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. When the formed 5-membered, 6-membered or 7-membered ring is a further substitutable group, it may be substituted with the substituent described for R _{31 to} R ₃₅ , and two or more substituents may be substituted. When substituted with a group, the substituents may be the same or different.
In the above 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, and have no substituent. When forming 6-membered and 7-membered saturated rings or 5-membered, 6-membered and 7-membered unsaturated rings, 5-membered, 6-membered and 7-membered saturated rings or 5-membered, 6-membered and 7-membered Examples of the unsaturated ring include 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 A ring, a pyrazine ring, and a pyridazine ring are mentioned, Preferably, a benzene ring and a pyridine ring are mentioned.

In particular, R ₃₂ and R ₃₃ are preferably hydrogen atoms, and R ₃₁ and R ₃₄ are preferably substituted or unsubstituted phenyl groups. 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.

<Counter-anion Y ^->
Y ^- is represents inorganic or organic anion, as long as it has an anionic ion, either 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.
Especially, what has the conjugate base of the organic acid which has a fluorine group containing phosphorus anion, a fluorine group containing boron anion, a cyano group containing nitrogen anion, and a halogenated hydrocarbon group is especially preferable from the surface of tolerance provision.

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 _{over, (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 ^{_{them, 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.

Fluorine group-containing boron anions 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, BF ₄ ⁻ , 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.

Cyano group-containing nitrogen anions include [(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. Of _{these, [(CN) 2 N]} - it is particularly preferred.

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.

  Specific examples of xanthene dyes include the following acidic dyes, oil-soluble dyes, basic dyes and the like, but are not limited thereto.

[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.

(Anthraquinone dye)
The anthraquinone dye is not limited as long as it has an anthraquinone skeleton, but the anthraquinone dye having a diaminoanthraquinone skeleton exhibits color development, color reproducibility, and high brightness while having heat resistance and light resistance. This is preferable. 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 dyes, the anthraquinone dyes represented by the general formulas (3-1), (3-2), and (3-3) are preferable because they are excellent in lightness and resistance.

General formula (3-1) General formula (3-2)

In 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 each independently represent a hydrogen atom, a hydroxyl group, -NHR ₄₉ (R ₄₉ and R ₄₁ has the same meaning), SO ₃ M group, a halogen atom, -COR '(R' is 1-3 carbon atoms Represents an alkyl group of
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 .

  As the “substituent”, 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, a trifluoromethyl group, nitro A monovalent to trivalent metal salt of an acidic group selected from a group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a 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 -Methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group, etc. However, it is not limited to these.

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

  Specific examples of the anthraquinone dyes 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 dyes)
Examples of the triarylmethane include diaminotriarylmethane dyes, triaminotriarylmethane dyes, rosic acid dyes having an OH group, and the like.
Triaminotriarylmethane-based dyes are preferable in that they have excellent color tone and are more excellent in fastness to sunlight than others. Among these, diphenylnaphthylmethane dye which is a basic dye is particularly preferable.
Triarylmethane-based dyes have high spectral characteristics in the wavelength range of 400 to 430 nm, and can be used not only for spectral characteristics but also for resistance when used as the dye monomer (A) of the present invention. An excellent colorant can be obtained.

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

General formula (4-1) General formula (4-2)

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. An alkenyl group, an optionally substituted phenyl group, or a fluorine atom is represented. 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 preferably hydrogen atoms.

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

  The “substituent” is the same as the “substituent” mentioned in the section of the anthraquinone dye.

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

  Specific examples of the triarylmethane dye include the following acidic dyes and basic dyes, but are not limited thereto.

[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.

<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 to use a salt formed with an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.
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, a salt-forming compound of an acid dye and / or a sulfonic acid amide compound of an acid dye is preferable because of its resistance and excellent compatibility with a pigment, and the acid dye is a counter component that works as a counter ion. It is more preferable to use a compound salted with a quaternary ammonium salt compound.

<Pigment (B)>
The pigment (B) contained in the photosensitive coloring composition of the present invention contains a phthalocyanine ring, and in addition, an organic or inorganic pigment can be mixed and used. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown with a color index number.
Examples of the pigment containing a phthalocyanine ring include C.I. Pigment Green 7, 36, 37 and 58 and other green pigments such as C.I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and 16 can be used.
Among these, from the viewpoint of fastness and color reproducibility, C.I. Pigment Blue 15: 6 is preferably included.
Further, other pigments not containing a phthalocyanine ring may be used in combination, for example, C.I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 144, 146, 149, 166, 168, 169, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, Red pigments such as 228, 240, 242, 246, 254, 255, 264, 272, 279,
For example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 , Yellow pigments such as 177,179,180,181,182,185,187,188,193,194,199,213,214,
For example, C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 and other orange pigments such as C.I. Pigment Green 10 and other green pigments such as C.I. Pigment Blue 22, 60, 64, 80, etc. Blue pigments such as C.I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, such as carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used.

Also, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The photosensitive coloring composition of the present invention may contain other dyes for color matching.

  Based on the total nonvolatile components of the photosensitive coloring composition of the present invention (100% by weight), the preferable concentration of the pigment (B) component is 10% by weight or more, more preferably from the viewpoint of obtaining sufficient color reproducibility. It is 15% by weight or more, and most preferably 20% by weight or more. Further, since the stability of the photosensitive coloring composition is improved, the preferable concentration of the pigment (B) component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less. is there.

[Miniaturization of pigment]
The pigment used in the present invention is preferably used after being refined, but the refinement method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used, and examples thereof are exemplified in the present invention. Thus, the salt milling process by the kneader method which is 1 type of wet grinding can be performed.

The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. 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 for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  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% by weight based on 100% 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, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, most preferably 50 to 500% by weight, based on 100% 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% by weight with respect to 100% by weight of the pigment.

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

  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 (C) 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.

  The content of the photopolymerizable monomer (C) is preferably 10 to 300% by weight and more preferably 10 to 200% by weight with respect to 100% by weight of the colorant from the viewpoint of photocurability and developability. It is preferable to use it in an amount.

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

  As the photopolymerization initiator (D), a conventionally known polymerization initiator can be used. Specifically, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane , Oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenones such as phenyl] -2-methylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Examples include glyoxylic methyl ester. More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01, IRGACURE OXE-02 (BASF), Adekaoptomer N1717, Adekaoptomer N1919, Adeka Arcles NCI- 831 (ADEKA), Esacure 1001M (Lamberti), Japanese Patent Publication No. 59-1281, Japanese Patent Publication No. 61-9621, and Triazine derivatives described in JP-A-60-60104, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, Japanese Patent Publication No. 47-1604 and diazonium compound publications described in US Pat. No. 3,567,453, USP No. 2,848,328, USP No. 2,852,379, and USP No. 2,940,853, organic azide compounds described in Japanese Patent Publication No. Sho 36- Ortho-quinonediazides described in JP-A-22062, JP-B-37-13109, JP-B-38-18015 and JP-B-45-9610, JP-B-55-39162, JP-A-59-140203 And `` MACROMOLECULES '', No. Vol. 0, various onium compounds including iodonium compounds described on page 1307 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851 EP-A-126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986), metal allene complexes described in JP-A-61-151197. Transition metals such as ruthenium described in JP-A-2-182701, as well as the titanocenes described in Japanese Patent Publication No. 1993, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) Transition metal complexes, aluminate complexes described in JP-A-3-209477, JP-A-2-1577 No. 60, borate compounds, JP-A Nos. 55-127550 and 60-202437, 2,4,5-triarylimidazole dimers, carbon tetrabromide and JP-A No. Nos. 59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977. Aminoketone compounds described in JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, JP-T-2004-534797, JP-A-2006-342166 , JP2008-094770, JP2009-40762, 2010-15025, JP 2010-189279, JP 2010-189280, JP 2010-526946, JP 2010-527338, JP 2010-527339, USP 3558309 (1971), USP 4202697 (1980) And oxime ester compounds described in JP-A No. 61-24558.

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

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

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

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

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

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. 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>
The color composition for a color filter of the present invention comprises a colorant containing the dye monomer (A) and the pigment (B) of the present invention in a colorant carrier composed of the resin and, if necessary, a solvent. Preferably, 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.

  The color composition for color filter of the present invention is produced by mixing the pigment monomer (A), pigment (B), and other colorants of the present invention separately dispersed in a colorant carrier. You can also. Further, when the solubility of the dye monomer (A) of the present invention is high, specifically, it is highly soluble in the solvent to be used. There is no need to manufacture it in a dispersed manner.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Next, the manufacturing method of the binder resin used for the Example and the comparative example is demonstrated.
(Acrylic resin solution (J-1))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 70.0 parts of propylene glycol monoethyl ether acetate, heated to 80 ° C., and the reaction vessel was filled with nitrogen. After substitution, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of styrene, 2,2′-azobisisobutyronitrile from the dropping tube. 0.4 parts of the mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Ether acetate was added to obtain an acrylic resin solution (J-1) which is an alkali-soluble resin.

(Acrylic resin solution (J-2))
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 (J-2) which is an energy ray curable resin having a bond was obtained.

<Preparation of resin-type dispersant solution>
A commercially available resin-type dispersant, EFKA4300 manufactured by BASF, and ethylene glycol monomethyl ether acetate were used to prepare a solution having a nonvolatile content of 40% by weight and used as a resin-type dispersant solution.

<Method for producing pigment monomer / precursor>
(Method for producing dye monomer / precursor STZ-1)
A dye monomer / precursor STZ-1 was prepared according to the description in JP-A-9-255882.
20 g of the raw material (1), 31 g of the raw material (2) and 9 g of zinc chloride were sequentially put in a flask and reacted at 140 to 160 ° C. for 2 hours. The reaction solution was poured into 100 ml of diluted hydrochloric acid, and the precipitated crystals were collected by filtration. After washing with water and drying, 23 g of STZ-1 was obtained. The structure was identified by NMR and mass spectrometry.

(Production Method of Dye Monomer / Precursor STZ-2)
STZ-2 was prepared in the same manner as STZ-1, except that the raw material (2) of the dye monomer / precursor STZ-1 was changed to the raw material (3).

<Method for producing pigment monomer>
(Production Method of Dye Monomer ST-1)
In a 1 L stainless steel reaction vessel equipped with a reflux tube, C.I. I. Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd .: Rhodamine B) is dissolved in 5.0 parts and 1.6 parts of hydroxyethyl methacrylate (HEMA) are dissolved in 40 ml of dichloromethane, and 1- (3-dimethylaminopropyl) -3-ethyl is dissolved. Carbodiimide hydrochloride (2.2 parts) and dimethylaminopyridine (0.25 part) were added, and the mixture was 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 ST-1. The yield was 51.6%.

(Production Method of Dye Monomer ST-2)
Dye monomer ST-2 was prepared in the same manner as Dye monomer ST-1, except that hydroxyethyl methacrylate (HEMA) was changed to 2-hydroxyethyl acrylate (HEA). The yield was 48.8%.

(Production Method of Dye Monomer ST-3)
Dye monomer ST-3 was prepared in the same manner as Dye monomer ST-1, except that hydroxyethyl methacrylate (HEMA) was changed to glycerin monomethacrylate (GLM). The yield was 49.1%.

(Production Method of Dye Monomer ST-4)
Dye monomer ST-4 was prepared in the same manner as Dye monomer ST-1, except that hydroxyethyl methacrylate (HEMA) was changed to glycerin dimethacrylate (GMR). The yield was 50.6%.

(Production Method of Dye Monomer ST-5)
1 part of the dye monomer ST-1 was dissolved in 100 ml of water, and 1.4 parts of sodium tetrafluoroborate (NaBF ₄ ) was added thereto, followed by stirring at room temperature for 2 hours. After filtration, washing with water and drying at 80 ° C., a dye monomer ST-5 was obtained. The yield was 87.8%.

(Production Method of Dye Monomer ST-6)
Dye monomer ST-6 was synthesized in the same manner as Dye monomer ST-5, except that sodium tetrafluoroborate (NaBF ₄ ) was changed to NaB (CF ₃ ) ₄ . The yield was 89.2%.

(Production Method of Dye Monomer ST-7)
Dye monomer ST-7 was synthesized in the same manner as Dye monomer ST-5, except that sodium tetrafluoroborate (NaBF ₄ ) was changed to the raw material (4) shown below. The yield was 83.5%.

(Production Method of Dye Monomer ST-8)
Other than changing the sodium tetrafluoroborate (NaBF ₄ ) to the following raw material (5) (Mitsubishi Materials Electronics Kasei Co., Ltd .: cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium salt) Dye monomer ST-8 was synthesized by the same method as that of monomer ST-5. The yield was 86.6%.

(Production Method of Dye Monomer ST-9)
In the production method of the dye monomer ST-5, the dye monomer ST-1 is changed to the dye monomer ST-3, and sodium tetrafluoroborate (NaBF ₄ ) is changed to NaB (C ₆ F ₅ ) ₄ Synthesize | combined dye monomer ST-9 by the method similar to dye monomer ST-5. The yield was 84.1%.

(Production Method of Dye Monomer ST-10)
C. I. Except for changing Basic Violet 10 (manufactured by Taoka Chemical Co., Ltd .: Rodamine B) to dye monomer / precursor STZ-1, dye monomer ST-10 was prepared in the same manner as dye monomer ST-1. It was created. The yield was 42.8%.

(Production Method of Dye Monomer ST-11)
C. I. Except for changing Basic Violet 10 (manufactured by Taoka Chemical Co., Ltd .: Rhodamine B) to the dye monomer / precursor STZ-2, the same procedure as for the dye monomer ST-1 was performed. It was created. The yield was 46.8%.

(Production Method of Dye Monomer ST-12)
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 ST-12. The yield was 46.8%.

(Production Method of Dye Monomer ST-13)
C. I. Solvent RED 172 to C.I. I. Dye monomer ST-13 was prepared in the same manner as Dye monomer ST-12, except that Solvent RED 222 (SR222: New Dragonindrital) was changed. The yield was 47.2%.

(Production Method of Dye Monomer ST-14)
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 raw materials (6) were obtained by removing a solvent with an evaporator.

  Next, 1.3 parts of phosphorus oxychloride was added to a mixture of 3 parts of raw material (6), 2.1 parts of raw material (7) 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 dye monomer ST-14.

(Production Method of Dye Monomer ST-15)
Dye monomer ST-15 was obtained using the same method as dye monomer ST-14 except that hydroxyethyl methacrylate in the production example of dye monomer ST-14 was changed to hydroxypropyl methacrylate. .

<Method for producing pigment monomer / dispersion solution>
(Production Method of Dye Monomer / Dispersion Solution P-1)
According to the following, after mixing various materials, the dye monomer / dispersion solution P-1 was obtained by performing ultrasonic irradiation for 1 hour.

Dye monomer ST-1: 4.0 parts Acrylic resin solution (J-1): 30.0 parts Cyclohexanone: 16.0 parts Total: 50.0 parts

(Production Method of Dye Monomer / Dispersion Solution P-2 to 16)
Except for changing the dye monomer ST-1 to the dye monomer shown in Table 2, the dye monomer / dispersion solution (P- 2-16) were produced.

BV10: C.I. I. Basic violet 10

<Production method of fine pigment>
(Blue fine pigment: PB15: 6)
Phthalocyanine blue pigment CI Pigment Blue 15: 6 (Toyocolor “LIONOL BLUE ES”, specific surface area 60 m ² / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a blue fine pigment (PB-1) were obtained.

(Purple fine pigment: PV23)
Dioxazine-based purple pigment CI Pigment Violet 23 (Toyocolor “LIONOGEN VIOLEET RL” 75 m ² / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a purple fine pigment (PV-1) were obtained.

(Red fine pigment: PR254)
Diketopyrrolopyrrole red pigment CI 200 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by BASF Japan Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of red fine pigment (PR-1) were obtained.

(Green fine pigment: PG36)
Phthalocyanine green pigment CI 200 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a green fine pigment (PG-1) were obtained.

(Yellow fine pigment: PY150)
Nickel complex yellow pigment CI 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a yellow fine pigment (PY-1) were obtained.

<Method for producing pigment dispersion>
(Pigment dispersion (N-1 to 5)
After stirring and mixing the mixture of the composition (parts by weight) shown in Table 3 so as to be uniform, it was 5 using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. After time dispersion, the mixture was filtered through a 5.0 μm filter to prepare pigment dispersions (N-1 to 5).

<Method for producing red and green resist materials>
(Red resist material (RR-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 (RR-1).
Red pigment dispersion (N-3): 50.0 parts Yellow pigment dispersion (N-5): 10.0 parts Acrylic resin solution (J1): 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ( Shin-Nakamura Chemical "NK ester ATMPT")
Photopolymerization initiator ("Irgacure 907" manufactured by BASF Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate: 23.2 parts

(Green resist material (GR-1))
A green resist material (GR-1) was obtained in the same manner as the red resist material (RR-1) except that the red pigment dispersion (N-3) was changed to the green pigment dispersion (N-4).

[Example 1]
(Blue coloring composition (DP-1))
The following mixture was stirred and mixed to be uniform, and then filtered through a 5.0 μm filter to obtain a colored composition (DP-1).
Dye monomer / dispersion solution (P-1): 2.4 parts Blue pigment dispersion (N-1): 8.6 parts acrylic resin solution (J2): 40.0 parts propylene glycol monomethyl ether acetate: 49. 0 copies

[Examples 2 to 13, Comparative Example 1]
(Blue coloring composition (DP-2 to 13, 16))
The blue colored composition (DP-1) was changed in the same manner as the blue colored composition (DP-1) except that the dye monomer / dispersed solution (P-1) was changed to the dye monomer / dispersed solution shown in Table 4, respectively. DP-2 to 13, 16) were adjusted.
However, Examples 12 and 13 are reference examples.

[Example 14]
(Blue coloring composition (DP-14))
The following mixture was stirred and mixed to be uniform, and then filtered through a 5.0 μm filter to obtain a colored composition (DP-14).
Dye monomer / dispersion solution (P-14): 2.8 parts Blue pigment dispersion (N-1): 8.2 parts Acrylic resin solution (J2): 40.0 parts Propylene glycol monomethyl ether acetate: 49. 0 copies
However, Example 14 is a reference example.

[Example 15]
(Blue coloring composition (DP-15))
The blue coloring composition (DP-15) was prepared in the same manner as the blue coloring composition (DP-14) except that the dye monomer / dispersion solution (P-14) was changed to (P-15). .
However, Example 15 is a reference example.

[Comparative Example 2]
(Blue coloring composition (DP-17))
The following mixture was stirred and mixed to be uniform and then filtered through a 5.0 μm filter to obtain a colored composition (DP-17).
Purple pigment dispersion (N-2): 0.4 part Blue pigment dispersion (N-1): 10.6 parts Acrylic resin solution (J2): 40.0 parts Propylene glycol monomethyl ether acetate: 49.0 parts

[Evaluation of blue coloring composition]
About the obtained coloring composition (DP-1-17), the color characteristic, tolerance (heat resistance, light resistance, solvent resistance) test, and the test regarding a coating-film foreign material were done by the following method. The results are shown in Table 5.

(Evaluation of color characteristics)
A colored composition obtained by coating the glass substrate with a film thickness such that the hue after heating at 230 ° C. for 20 minutes was x = 0.140 and y = 0.06 with a C light source was produced. . Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.

◎ ... 5.6 or more ○ ... 5.3 or more and less than 5.6 Δ ... 5.0 or more and less than 5.3 × ... less than 5.0

(Coating film heat resistance test)
The obtained colored composition (DP-1 to 18) was applied on a glass substrate so that the film thickness was 2.0 μm, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured using a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Further, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.

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 heat resistance of the coating film was evaluated in the following four stages.
◎: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0 Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

(Coating light resistance test)
A test substrate was prepared in the same procedure as the coating heat resistance test, and the chromaticity 1 (L * (1), a * (1), b * (1)) under a C light source was changed to a microscopic spectrophotometer. Measurement was performed using a meter (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). Thereafter, the substrate was placed in a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI) and left for 500 hours. After removing the substrate, chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured. Using these chromaticity values, the color difference ΔEab * was calculated in the same manner as in the coating film heat resistance test, and the light resistance of the coating film was evaluated in four stages according to the same criteria as for heat resistance.

  As shown in Table 5, the blue coloring compositions (DP-1 to 15) for color filters of the present invention containing the dye monomers ST-1 to 15 having a specific structure are both high in lightness and resistant. It was excellent.

  On the other hand, in the blue coloring composition (DP-16), since the dye monomer BV10 does not contain a specific structure, the change in heat-resistant color difference exceeded 5. The blue coloring composition (DP-17) uses a dioxazine pigment that has been suitably used in the past. There was no problem with tolerance, but the value was low.

[Example 16]
(Blue resist material (BR-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 type blue resist material (R-1).

Dye monomer / dispersion solution (P-1): 13.0 parts Blue pigment dispersion (N-1): 47.0 parts Acrylic resin solution (J2): 11.0 parts Trimethylolpropane triacrylate: 4. 2 parts (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF Japan): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 23.2 parts

[Examples 17 to 28, Comparative Example 3]
(Blue resist material (BR-2 to 13, 17))
The blue colored composition (BR) is the same as the blue resist material (BR-1) except that the dye monomer / dispersion solution (P-1) is changed to the dye monomer / dispersion solution shown in Table 6, respectively. -2 to 13, 17) were adjusted.
However, Examples 27 and 28 are reference examples.

[Example 29]
(Blue resist material (BR-14))
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain an alkali developing blue resist material (BR-14).
Dye monomer / dispersion solution (P-14): 15.4 parts Blue pigment dispersion (N-1): 44.6 parts acrylic resin solution (J-2): 11.0 parts trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd. “NK Ester ATMPT”)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF Japan): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 23.2 parts
However, Example 29 is a reference example.

[Example 30]
(Blue resist material (BP-15))
A blue resist material (BP-15) was prepared in the same manner as the blue resist material (BR-14) except that the dye monomer / dispersion solution (P-14) was changed to (P-15).
However, Example 30 is a reference example.

[Example 31]
(Blue resist material (BR-16))
After stirring and mixing the following mixture uniformly, it is filtered through a 1.0 μm filter,
An alkali development type blue resist material (BR-16) was obtained.
Dye monomer / dispersion solution (P-15): 15.4 parts Blue pigment dispersion (N-1): 44.6 parts Acrylic resin solution (J2): 10.0 parts Trimethylolpropane triacrylate: 4. 1 part (Shin Nakamura Chemical Co., Ltd. “NK ESTER ATMPT”)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Antioxidant: Phenol antioxidant penta Erythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate: 0.5 part cyclohexanone: 23.8 parts
However, Example 31 is a reference example.

[Comparative Example 4]
(Blue resist material (BR-18))
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 blue resist material (BR-18).

Purple pigment dispersion (N-2): 2.1 parts Blue pigment dispersion (N-1): 57.9 parts Acrylic resin solution (J2): 11.0 parts Trimethylolpropane triacrylate: 4.2 parts ( Shin-Nakamura Chemical "NK ester ATMPT")
Photopolymerization initiator ("Irgacure 907" manufactured by BASF Japan): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 23.2 parts

[Evaluation of blue resist material]
The color characteristics and resistance (heat resistance, light resistance) of the blue resist materials (BR-1 to 18) were evaluated using the same method as that for the blue coloring composition. The results are shown in Table 7.

  Similar to the evaluation results of the blue coloring composition, each of the blue resist materials (BR-1 to 16) of the present invention containing the dye monomers ST-1 to 15 having a specific structure has high lightness and resistance. It was excellent.

  On the other hand, in the blue resist material (BR-17), since the dye monomer BV10 does not contain a specific structure, the change in heat-resistant color difference exceeds 5. The blue resist material (BR-18) uses a dioxazine pigment that has been used preferably. There was no problem with tolerance, but the value was low.

[Preparation of color filter]
A black matrix is patterned on a glass substrate, and a red resist material (RR-1) is applied on the substrate with a spin coater so that x = 0.640 and y = 0.330 with a C light source. A colored coating was formed. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. In the same manner, the green resist material (GR-1) is formed to have a film thickness such that x = 0.300 and y = 0.600 in the C light source, and the blue resist material (BR-1) is used in the C light source. The film was applied in such a film thickness that x = 0.140 and y = 0.060, respectively, to form a green filter segment and a blue filter segment to obtain a color filter (CF-1).

  About the color filter produced as mentioned above, high brightness and good fastness could be confirmed for each of blue and white.

  As described above, a blue colored composition for a color filter containing a dye monomer having a specific structure can obtain a blue filter segment with high brightness and excellent heat resistance and light resistance.

Claims (5)

A color filter coloring composition comprising a colorant, a resin, and a solvent, wherein the colorant comprises a dye monomer (A) represented by the following general formula (1), a pigment (B), containing, pigment (B) is, only contains the phthalocyanine skeleton,
Unsaturated monobasic resin having an unsaturated ethylenic double bond on the side chain epoxy group of a copolymer of an unsaturated ethylenic monomer having an epoxy group and one or more other monomers A colored composition for a color filter, which is a resin obtained by reacting a polybasic acid anhydride with a hydroxyl group produced by addition reaction of a carboxyl group of an acid .

General formula (1)
[In general formula (1), Q represents a xanthene skeleton represented by the following general formula (2).
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 - represents a.
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 — is represented. 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 —. ]

General formula (2)
[In the general formula (2), R ₃₁ ~R ₃₄ each independently represent a hydrogen atom or a monovalent substituent, 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 pigment (B) is C.I. I. The blue coloring composition for a color filter according to claim 1, which is CI Pigment Blue 15: 6. The colored composition for a color filter according to claim 1 or 2, further comprising a photopolymerizable monomer (C) and / or a photopolymerization initiator (D). Furthermore, antioxidant (E) is contained, The coloring composition for color filters of any one of Claims 1-3 characterized by the above-mentioned. A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 1 on a substrate.