JP2015018195A - Colored composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter, which shows high brightness and has excellent heat resistance while causing no crystallization in a process of forming a color filter, and to provide a color filter using the above composition excellent in color characteristics and heat resistance.SOLUTION: The colored composition for a color filter comprises a colorant, a resin and a solvent. The composition is a red colored composition for a color filter, in which the colorant comprises a dye monomer (A1) expressed by general formula (1) and an organic pigment (B); and the organic pigment (B) comprises at least one pigment selected from a group consisting of a diketopyrrolopyrrole pigment (B1) and an azo pigment (B2).

Description

  The present invention relates to a coloring composition comprising a dye monomer (A1), an organic pigment (B), a solvent, and a resin, and more specifically, solvent solubility and fastness (heat resistance, light resistance, solvent resistance). ) And a color composition that can be suitably used for a color display plate, etc., preferably for a color filter used in the production of a color filter used in a color liquid crystal display device, an organic EL display device, a color imaging tube element, etc. With regard to the color filter coloring composition and the color filter, the coloring composition of the present invention can be applied to red, green, and blue color filters.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. In recent years, since it has been used for televisions, personal computer monitors, and the like, demands for a wide color reproduction region and high reliability are increasing along with high contrast and high brightness for color filters.

  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 that vertically aligns nematic liquid crystal with optical properties, and optically converged bend (OCB) method that optically compensates by making the optical axes of uniaxial retardation films orthogonal to each other Etc., and each has been put to practical use.

  In general, a color filter is formed in a fine strip (stripe) shape formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) are arranged in parallel or intersecting with each other, or the fine filter segments are arranged in a constant vertical and horizontal arrangement. 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. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) is also used.

  One of the quality items required for the color filter is brightness. When 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 that are 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.

Also, C-MOS (Complementary Metal Oxide Semico
A color imaging tube element typified by nductor (complementary metal oxide semiconductor), CCD (Charge Coupled Device) or the like has a red filter layer (R), a green filter layer (G) and a light receiving element on the light receiving element. In general, color separation is performed by disposing color filters each having an additive mixed primary color filter segment of the blue filter layer (B). Further, since high sensitivity can be obtained compared to the primary color filter, a color filter having filter segments of cyan, magenta, and yellow (CMY) corresponding to the complementary colors of red, green, and blue is often used. Complementary color filters are often used in video cameras and the like that are difficult to use an auxiliary light source such as a flash.
In recent years, there has been an increasing demand for high transmittance, that is, lightness and high reliability even in color filters used in color image pickup tube elements.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dye dispersion method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  Conventionally, an anthraquinone pigment (for example, CI Pigment Red 177) or a diketopyrrolopyrrole pigment (for example, CI Pigment Red 254) has been used as a colorant used for forming a red filter segment. It was. These pigments can be easily refined by mechanical treatment, and further, the refined pigment can be dispersed relatively easily. Therefore, these pigments are useful for improving contrast and brightness. Furthermore, in order to achieve high brightness and a wide color reproduction range, these red pigments and C.I. I. In general, yellow pigments such as CI Pigment Yellow 138, 139, 150, and 185 are used in combination as a colorant.

As a colorant used for forming a green filter segment, a copper halide phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment Green 7) has been conventionally used. A zinc halide phthalocyanine pigment (for example, CI Pigment Green 58), which is a color material that exhibits a wide color display area and has high coloring power, has been often used. Furthermore, in order to achieve high brightness and a wide color reproduction range, these green pigments and C.I. I. It is common to use yellow pigments such as CI Pigment Yellow 138, 139, 150, and 185 in combination.

  The colorant used for forming the blue filter segment is generally used in combination with a copper phthalocyanine pigment and a dioxazine pigment.

  In addition, in order to cope with high brightness demanded in recent years, a technique for dissolving a dye instead of a pigment as a colorant in a resin or the like has been proposed (for example, see Patent Document 1). However, using only the dye itself such as a direct dye or an acid dye, although the color developability is good, it is inferior in heat resistance and light resistance, and is not satisfactory. (For example, see Patent Document 2)

  As described above, dyes have many advantages over pigments, but no dyes having both fastness and color characteristics (lightness) have been developed, and further improvements are required.

JP-A-6-75375 JP-A-8-327811 Japanese Patent No. 4492760 JP 2000-162429 A JP 2000-154206 A JP 2012-32754 A

  An object of the present invention is to provide a coloring composition for a color filter that satisfies fastness and has excellent color characteristics (brightness) and an excellent contrast ratio, 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 present inventors have obtained a dye monomer (A1) represented by the general formula (1) and a specific organic pigment (B). It has been found that the above-mentioned problems are solved by the coloring composition to be included.

［一般式（１）中、Ｑは有機色素骨格を表す。
Ｘは、直接結合、−Ｒ₂−、−ＮＨ−Ｒ₃−、−Ｏ−Ｒ₃−、−ＣＯ−Ｒ₃−、−ＣＯＯ−Ｒ₃−、または−Ｏ−ＣＯ−Ｒ₃−を表す。
Ｒ₁は、水素原子、またはメチル基を表す。
Ｒ₂は、置換もしくは無置換のアルキレン基、置換もしくは無置換のエステル結合（−ＣＯＯ−）およびエーテル結合（−Ｏ−）から選ばれる一種類以上の結合を少なくとも１つ含むアルキレン基、置換もしくは無置換のアルケニレン基、置換もしくは無置換のアリーレン基、−Ｒ₄−Ｏ−Ｒ₅−、−Ｒ₄−ＣＯ−Ｒ₅−、−Ｒ₄−ＣＯＯ−Ｒ₅、−Ｒ₄−Ｏ−ＣＯ−Ｒ₅−、−Ｒ₄−Ｏ−ＣＯＮＨ−Ｒ₅−、または−Ｒ₄−Ｏ−ＣＯ−Ｒ₆−ＣＯ−Ｒ₅−を表す。
Ｒ₃は、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルケニレン基、置換もしくは無置換のアリーレン基、−Ｒ₄−Ｏ−Ｒ₅−、−Ｒ₄−ＣＯ−Ｒ₅−、−Ｒ₄−Ｏ−ＣＯ−Ｒ₅−、−Ｒ₄−Ｏ−ＣＯＮＨ−Ｒ₅−、または−Ｒ₄−Ｏ−ＣＯ−Ｒ₆−ＣＯ−Ｒ₅−を表す。Ｒ₄およびＲ₆は、それぞれ独立に、置換もしくは無置換のアルキレン基、置換もしくは無置換のアルケニレン基、または置換もしくは無置換のアリーレン基を表す。Ｒ₅は、置換もしくは無置換のアルキレン基、または−Ｏ−ＣＨ₂−ＣＨＯＨ−ＣＨ₂−を表す。］ 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 (A1) represented by the following general formula (1): An organic pigment (B), and the organic pigment (B) contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment (B1) and an azo pigment (B2). The present invention relates to a color filter coloring composition.
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—) and 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 general formula (2), an anthraquinone skeleton represented by the general formula (3-1), or a general formula (3-2). And an anthraquinone skeleton represented by general formula (3-3) and at least one organic dye skeleton selected from the group consisting of the anthraquinone skeleton represented by formula (3-3).

[一般式（２）中、Ｒ₃₁〜Ｒ₃₄は、各々独立に、水素原子又は１価の置換基を表し、Ｒ₃₁とＲ₃₂、およびＲ₃₃とＲ₃₄は、環構造を形成しても良い。Ｒ₃₅は、各々独立に、１価の置換基を表し、ｍは、０から５の整数を表す。Ｙ^-は、無機または有機のアニオンを表す。
ここで、Ｒ₃₁〜Ｒ₃₅のいずれか１つは、Ｘとの結合手である。] 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. ]

［一般式（３−１）、（３−２）、および（３−３）中、
Ｒ₄₁は水素原子、−ＲＯＨ（Ｒは炭素数１〜５のアルキレン基）、−ＲＣＯＯＨ（Ｒは炭素数１〜５のアルキレン基）、または置換基を有してもよいフェニル基を表す。Ｒ₄₂〜Ｒ₄₈は、各々独立に水素原子、水酸基、−ＮＨＲ₄₉（Ｒ₄₉とＲ₄₁は同義である）、ＳＯ₃Ｍ基、ハロゲン原子、−ＣＯＲ’（Ｒ’は炭素数１−３のアルキル基を表す）である。
ここで、Ｒ₄₁〜Ｒ₄₈のいずれか１つは、Ｘとの結合手である。］ General formula (3-1), (3-2), (3-3):

[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. ]

  In the present invention, the diketopyrrolopyrrole pigment (B1) is a diketopyrrolopyrrole pigment (b1) represented by the following general formula (4) and a diketopyrrolopyrrole pigment represented by the following general formula (5) ( It contains at least one selected from the group consisting of b2).

[一般式（５）中、Ｘは塩素原子、または臭素原子を表し、ＢおよびＤは、それぞれ独立して、水素原子、フッ素原子、ヨウ素原子、シアノ基、炭素数１〜１２のアルキル基、置換基を有してもよいフェニル基、−ＣＦ₃、−ＯＲ¹³、−ＳＲ¹⁴、−Ｎ（Ｒ¹⁵）Ｒ¹⁶、−ＣＯＯＲ¹⁷、−ＣＯＮＨ₂、−ＣＯＮＨＲ¹⁸、−ＣＯＮ（Ｒ¹⁹）Ｒ²⁰、−ＳＯ₂ＮＨ₂、−ＳＯ₂ＮＨＲ²¹、または、−ＳＯ₂Ｎ（Ｒ²²）Ｒ²³であり、Ｒ¹³〜Ｒ²³は、それぞれ独立して、炭素数１〜１２のアルキル基、置換基を有してもよいフェニル基、または、置換基を有してもよいアラルキル基である。ただし、ＢおよびＤが同時に水素原子になることはない。] General formula (4), (5):

[In General Formula (5), X represents a chlorine atom or a bromine atom, and B and D are each independently a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, An optionally substituted phenyl group, —CF ₃ , —OR ¹³ , —SR ¹⁴ , —N (R ¹⁵ ) R ¹⁶ , —COOR ¹⁷ , —CONH ₂ , —CONHR ¹⁸ , —CON (R ¹⁹ ) R ²⁰ , —SO ₂ NH ₂ , —SO ₂ NHR ²¹ , or —SO ₂ N (R ²² ) R ²³ , wherein R ^{13 to} R ²³ are each independently an alkyl group having 1 to 12 carbon atoms. A phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, B and D do not become hydrogen atoms at the same time. ]

  In the present invention, the diketopyrrolopyrrole pigment (b2) represented by the general formula (5) has the following general formula (5-1), the following general formula (5-2), and the following general formula (5-3). Or a coloring composition for a color filter as described above, which is any one of the following general formula (5-4):

[一般式（５−１〜５−４）中、Ｘは塩素原子、または臭素原子を表し、Ｒ²⁴〜Ｒ²⁶は、それぞれ独立して、炭素数１〜１２のアルキル基、または置換基を有してもよいフェニル基である。] Formulas (5-1) to (5-4):

[In the general formulas (5-1 to 5-4), X represents a chlorine atom or a bromine atom, and R ^{24 to} R ²⁶ each independently represents an alkyl group having 1 to 12 carbon atoms or a substituent. It is a phenyl group which may have. ]

  In the present invention, the diketopyrrolopyrrole pigment (B1) is C.I. I. Pigment Red 254 is contained, It is related with the said coloring composition for color filters characterized by the above-mentioned.

  In the present invention, the diketopyrrolopyrrole pigment (B1) includes the diketopyrrolopyrrole pigment (b2) represented by the general formula (5), and the diketopyrrolopyrrole represented by the general formula (5). The content of the pigment (b2) is 1 to 15% by weight in 100% by weight of the diketopyrrolopyrrole pigment (B1).

General formula (5):

  In the present invention, the azo pigment (B2) is C.I. I. Pigment red 166, C.I. I. Pigment red 221, C.I. I. Pigment red 242, and C.I. I. It is at least 1 sort (s) chosen from the group which consists of pigment orange 38, It is related with the said coloring composition for color filters characterized by the above-mentioned.

  The present invention also relates to the color composition for color filters described above, further comprising a photopolymerizable monomer (D) and / or a photopolymerization initiator (E).

  Moreover, this invention relates to the coloring composition for said color filters characterized by the photoinitiator (E) containing an oxime ester system photoinitiator (E1).

  In addition, the present invention relates to the color composition for a color filter as described above, wherein the oxime ester photopolymerization initiator (E1) has a carbazole group.

  The present invention also relates to the color filter coloring composition described above, further comprising an antioxidant (F).

  In the present invention, the antioxidant (F) is at least one oxidation selected from the group consisting of a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. The color filter coloring composition as described above, which is an inhibitor.

  In the present invention, the content of the antioxidant (F) is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for color filter. It is related with the coloring composition for color filters of description.

  The present invention also relates to a color filter comprising at least one filter segment made of the color filter coloring composition described above, wherein the color filter includes at least a red filter segment, a green filter segment, and a blue filter segment.

  According to the present invention, it is possible to provide a coloring composition for a color filter that satisfies both solvent solubility and fastness (heat resistance and light resistance). Furthermore, a color filter having a high brightness, a high contrast ratio, and a high sensitivity can be formed by preparing a color filter using the coloring composition for a color filter.

Hereinafter, embodiments of the present invention will be described in detail.
The coloring composition for a color filter of the present invention contains a dye monomer (A1) represented by the general formula (1), a specific organic pigment (B), a binder resin, and a solvent.

<Colorant>
(Dye monomer (A1))
The coloring composition for color filters of this invention contains the pigment | dye monomer (A1) described by General formula (1) as a coloring agent. It is also preferable to use an organic pigment (B) in combination. The dye monomer (A1) 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 to the terminal, 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 —.

  In the present invention, the “substituent” 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 trifluoro. Monovalent to trivalent metal of an acidic group selected from methyl 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 Salt (for example, sodium salt, potassium salt, aluminum salt etc.) etc. are mentioned. 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 dye compounds that can form a dye 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 and anthraquinone 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. It is preferable to use a direct dye, an oil-soluble dye, or a basic dye because of excellent reactivity and easy production of the dye monomer (A1).

  Among the xanthene-based and anthraquinone-based organic pigments, Q is at least one selected from the group consisting of a xanthene-based dye represented by the general formula (2) and an anthraquinone-based dye represented by the general formula (3). Is preferable because it is excellent in transparency and contrast ratio.

(Xanthene dyes)
Xanthene dyes are dyes containing a xanthene ring, and are roughly 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 member 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, but are not limited to, the following acidic dyes, oil-soluble dyes, and basic dyes.

[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)-(3-3):

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.

<Method for Producing Dye Monomer (A1)>
As a method for synthesizing the dye monomer (A1) 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 (A1) 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 (A1) 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 (A1) 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 (A1))
Although the dye monomer (A1) has good spectral characteristics and excellent color developability, it 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 sulfonamide compound after sulfonamidation.

  Among these, a salt forming compound of an acid dye and / or a sulfonic acid amide compound of an acid dye are preferable because they are excellent in resistance and combined use with a pigment, and an 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.

<Organic pigment (B)>
(Diketopyrrolopyrrole pigment (B1))
The diketopyrrolopyrrole pigment (B1) in the present invention includes the diketopyrrolopyrrole pigment (b1) represented by the general formula (4) (sometimes referred to as brominated diketopyrrolopyrrole pigment), and the general formula (5). And at least one diketopyrrolopyrrole pigment (b2) (sometimes referred to as a specific heterodiketopyrrolopyrrole pigment).
Among them, the case where both the diketopyrrolopyrrole pigment (b1) and the diketopyrrolopyrrole pigment (b2) are included is preferable because of excellent heat resistance.

  The content of the diketopyrrolopyrrole pigment (B1) of the present invention is 10 to 90% by weight, preferably 20 to 80% by weight, out of a total of 100% by weight of the colorant (A1), from the viewpoint of the color gamut. .

[Diketopyrrolopyrrole Pigment (b1) Represented by Formula (4)]
Formula (4):

  The brominated diketopyrrolopyrrole pigment that is the diketopyrrolopyrrole pigment (b1) can be obtained by using a known method described in International Publication No. 2009/144115 pamphlet or the like.

  As an example of the production method, it can be produced by a succinic acid diester synthesis method or the like. That is, 2 moles of 4-bromobenzonitrile per mole of succinic acid diester in an inert organic solvent such as tert-amyl alcohol in the presence of an alkali metal or an alkali metal alkoxide at a high temperature of 80 to 110 ° C. Performing a condensation reaction to produce an alkali metal salt of a diketopyrrolopyrrole compound, and then protonating the alkali metal salt of the diketopyrrolopyrrole compound with water, alcohol, acid, etc. Brominated diketopyrrolopyrrole pigments can be obtained. At this time, the size of the primary particle diameter obtained can be controlled by the temperature in protonation, the type, ratio and amount of water, alcohol or acid. The production method of the brominated diketopyrrolopyrrole pigment is not limited to this method.

  The diketopyrrolopyrrole pigment (b1) is C.I. I. It tends to be superior to CI Pigment Red 254. This is presumably because the bromo group has a higher molecular weight than the chloro group and the steric hindrance effect works.

  The content of the diketopyrrolopyrrole pigment (b1) is preferably in the range of 20 to 100% by weight in the total weight of 100% by weight of the diketopyrrolopyrrole pigment (B1). When the content of the diketopyrrolopyrrole pigment (b1) is within this range, the heat resistance and lightness are favorable.

[Diketopyrrolopyrrole Pigment (b2) Represented by General Formula (5)]
General formula (5):

In General Formula (5), X represents a chlorine atom or a bromine atom, and B and D are each independently a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or a substituent. a phenyl group which may have a ^{_{group, -CF 3, -OR 13, -SR}} 14, -N (R 15) R 16, -COOR 17, -CONH 2, -CONHR 18, -CON (R 19) R ²⁰ , —SO ₂ NH ₂ , —SO ₂ NHR ²¹ , or —SO ₂ N (R ²² ) R ²³ , wherein R ^{13 to} R ²³ are each independently an alkyl group having 1 to 12 carbon atoms, A phenyl group which may have a substituent or an aralkyl group which may have a substituent. However, B and D do not become hydrogen atoms at the same time.

  The alkyl group having 1 to 12 carbon atoms may be linear or branched, and specifically includes a methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group. Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, etc., but are not limited thereto. .

  Examples of the phenyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, and an alkoxyl having 1 to 4 carbon atoms. And a phenyl group having a substituent such as a group. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl Examples thereof include, but are not limited to, a phenyl group.

  Specific examples of the aralkyl group that may have a substituent include a benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, and 2,4- Examples include, but are not limited to, a dichlorobenzyl group.

Among the specific heterodiketopyrrolopyrrole pigments represented by the general formula (5) used in the pigment composition of the present invention, the general formula (5-1), the general formula (5-2), and the general formula (5- 3) and General Formula (5-4) are preferable from the viewpoints of brightness, contrast ratio, and crystal precipitation suppression effect. In addition, R ^{6 to} R ⁸ in the general formula (5-3) and the general formula (5-4) are an alkyl group having 4 or more carbon atoms, or a phenyl group which may have a substituent. It is preferable from the point of the suppression effect. The reason why these are effective in increasing contrast and suppressing crystal precipitation is because of the steric hindrance effect due to bulky substituents such as carboamide groups, phenyl groups, and t-butyl groups having an alkyl group having 4 or more carbon atoms. This is thought to be due to the suppression of aggregation. In addition, the specific heterodiketopyrrolopyrrole pigment having a carboamide group, a phenyl group, or a t-butyl group is excellent in color characteristics, and therefore, the brightness is hardly impaired.

Formulas (5-1) to (5-4):

In the general formulas (5-1) to (5-4), X represents a chlorine atom or a bromine atom, and R ^{24 to} R ²⁶ each independently represents an alkyl group having 1 to 12 carbon atoms or a substituent. It may be a phenyl group.

  Specific examples of the specific heterodiketopyrrolopyrrole pigment of the general formula (5) that can be used in the present invention are shown below, but are not limited thereto.

Formulas (5-1a), (5-2a), (5-3a), (5-3b), (5-3c) (5-3d):

Formula (5-3e), (5-3f), (5-3g), (5-4a), (5-4b), (5-5)

Formulas (5-6), (5-7), (5-8), (5-9a), (5-9b), (5-9c):

Formulas (5-10), (5-11), (5-12), (5-13), (5-14), (5-15):

Formula (5-16), (5-17), (5-18), (5-19), (5-20), (5-21):

Formula (5-22):

  Among the specific heterodiketopyrrolopyrrole pigments represented by formula (5) used in the colorant of the present invention, formula (5-1a), formula (5-2a), formula (5-4b), formula (5) -19) is preferable from the viewpoints of brightness and crystal precipitation suppression effect.

  The content of the specific hetero diketopyrrolopyrrole pigment (b2) represented by the general formula (5) is in the range of 1 to 15% by weight in 100% by weight of the total weight of the diketopyrrolopyrrole pigment (B1). Is preferred. When the content of the diketopyrrolopyrrole pigment (b2) is 1% by weight or more, the crystal precipitation suppressing effect is sufficient. In addition, when the content of the diketopyrrolopyrrole pigment (b2) is 15% by weight or less, the crystal precipitation suppressing effect is high and the brightness is sufficient.

  When the crystal precipitation suppressing effect is not sufficient, light scattering occurs due to the crystalline foreign matter deposited on the surface of the coating film in the heating step, causing a decrease in brightness and contrast ratio. Therefore, by using a red coloring composition containing the specific hetero diketopyrrolopyrrole pigment in the above content, a high brightness and a high contrast ratio are achieved, which is a problem when using a diketopyrrolopyrrole pigment in the heating process. The existing crystal precipitation can be solved.

[Other diketopyrrolopyrrole pigments]
The colorant of the present invention includes the diketopyrrolopyrrole pigment (b1) of the formula (4) and the specific heterodiketopyrrolopyrrole pigment (b2) of the general formula (5) as long as the effects of the present invention are not impaired. Other diketopyrrolopyrrole pigments may be used in combination. Specifically, C.I. I. Pigment red 254, 255, 264, 272, C.I. I. Examples thereof include, but are not limited to, diketopyrrolopyrrole pigments such as CI Pigment Orange 71, 73, or 81. As a diketopyrrolopyrrole pigment that can be used in combination, C.I. I. Pigment Red 254 is preferred.

  In the colorant of the present invention, diketopyrrolopyrrole pigment (b1) represented by the general formula (4) and C.I. I. When using together with pigment red 254, it is preferable that content of diketopyrrolopyrrole pigment (b1) is 20 to 99 weight% in 100 weight% of diketopyrrolopyrrole pigment (B1). When the total content of the diketopyrrolopyrrole pigment (b1) is less than 20% by weight, it may be difficult to impart heat resistance.

  In the colorant of the present invention, the specific heterodiketopyrrolopyrrole pigment (b2) represented by the general formula (5) and C.I. I. When using together with pigment red 254, it is preferable that content of diketopyrrolopyrrole pigment (b2) is 1 to 15 weight% in 100 weight% of diketopyrrolopyrrole pigment (B1). If it is less than 1% by weight, it is difficult to impart heat resistance, and if it exceeds 15% by weight, the brightness may be lowered.

  When considering various characteristics of lightness, heat resistance, and color gamut, as a coloring agent, a dye monomer (A1) represented by the general formula (1) and a diketopyrrolopyrrole represented by the formula (4) It is desirable to include three types of pigment (b1) and diketopyrrolopyrrole pigment (b2) represented by the general formula (5), and the blending ratio of each is 20 to 60% by weight / 30 to 75% by weight / 0. Most preferably, it is contained at 3 to 12% by weight. If the dye monomer (A1) and the diketopyrrolopyrrole pigment (b1) are out of this range, the color reproduction range may be limited, and the diketopyrrolopyrrole pigment (b2) is 0.3 weight. If it is less than%, the heat resistance may be affected by the lightness if it exceeds 12% by weight.

[Azo-based pigment (B2)]
The azo pigment (B2) of the present invention is an azo pigment exhibiting red, orange, and yellow. I. Pigment red, and C.I. I. Examples of the azo pigments belonging to Pigment Orange include azo pigments such as azo, disazo, and polyazo.
Examples of such pigments include C.I. I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 95, 112, 114, 119, 136, 144, 164, 166, 170, 171, 175, 176, 185, 208, 213, 214, 220, 221, 242, 253, 256, 258, C.I. I. Pigment Orange 1, 4, 15, 16, 22, 24, 38, 74 and the like. Among these, from the viewpoint of hue, brightness, and contrast ratio, C.I. I. Pigment red 166, 221, 242, C.I. I. Pigment Orange 38 is desirable.

By reducing the difference in refractive index between the pigment carrier made of pigment and resin, light scattering generated at the interface between the pigment and the pigment carrier can be suppressed, and high contrast can be achieved. Since the refractive index of a pigment carrier made of a resin, an organic solvent, or the like used for a color filter coloring composition is generally about 1.6 to 1.7, light of 600 to 700 nm is used as a colorant. By including a red azo pigment having a maximum refractive index of 1.8 or less in the wavelength region, a colored composition for a color filter having excellent stability and a high contrast ratio can be obtained.
(Other colorants)
In the present invention, since the hue can be easily adjusted, other red pigments, orange pigments, yellow pigments, and dyes other than the dye monomer (A1), diketopyrrolopyrrole pigment, and azo pigment in the present invention. May be used in combination. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

  Other colorants that can be used for these are described below.

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

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

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

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

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

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

[Miniaturization of pigment]
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 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

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

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

<Photopolymerizable monomer (D)>
The photopolymerizable monomer (D) 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.

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

<Photopolymerization initiator (E)>
The colored composition for a color filter of the present invention can be cured using radicals generated from the photopolymerization initiator (E) by ultraviolet irradiation or heat irradiation. It is preferable that the compounding quantity at the time of using a photoinitiator is 5-200 weight part with respect to 100 weight part of pigment | dye monomers (A1), and is 10-150 weight part from a photocurable viewpoint. It is more preferable.

  As the photopolymerization initiator (E), 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 (CGI124), IRGACURE OXE-02, Adekaoptomer N1414, Adekaoptomer N1717, Adekaoptomer N1919, Adeka Arcles NCI-831E, sacure1001M (Lamberti), Japanese Examined Patent Publication No.59-1281, Japanese Examined 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- Organic azide compounds described in Japanese Patent No. 6413, Japanese Patent Publication No. 47-1604 and US Pat. No. 3,567,453, diazonium compound publication, USP 2,848,328, USP 2,852,379 and USP 2,940,553, Ortho-quinone diazides described in JP-B 36-22062, JP-B 37-13109, JP-B 38-18015 and JP-B 45-9610, JP-B 55-39162, JP-A 59 -140203 and "Macromolecules (MACR OMOLECULES), Vol. 10, page 1307 (1977) and various onium compounds including azo compounds described in JP-A-59-142205, JP-A-1-54440, European patent No. 1099851, European Patent No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986), The titanocenes described in JP-A-61-151197, “COORDINATION CHEMISTRY REVIEW”, Vol. 84, pages 85-277 (1988) and ruthenium described in JP-A-2-182701. Transition metal complexes containing a transition metal such as JP-A-3-209477, Borate compounds described in JP-A-2-157760, 2,4,5-triarylimidazole dimers described in JP-A-55-127550 and JP-A-60-202437, carbon tetrabromide, Organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-54-99185, JP-A-63-264560, and JP-A Aminoketone compounds described in JP-A No. 10-29977, JP-A No. 2001-264530, JP-A No. 2001-261761, JP-A No. 2000-80068, JP-A No. 2001-233842, JP-T No. 2004-534797, JP-A No. 2004-34797 2006-342166, JP2008-094770, JP2009- 0762, JP 2010-15025, JP 2010-189279, JP 2010-189280, JP 2010-526846, JP 2010-527338, JP 2010-527339, USP 3558309 (1971), USP 4202697 Examples thereof include oxime ester compounds described in the description (1980) and JP-A No. 61-24558.

(Oxime ester photoinitiator (E1))
It is preferable that the coloring composition for color filters of this invention contains an oxime ester system photoinitiator (E1) as a photoinitiator (E).

  The oxime ester photoinitiator (E1) absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. Thereby, it becomes the coloring composition for color filters which is excellent in heat resistance, and is high brightness and high CR.

[Oxime ester photopolymerization initiator represented by general formula (6)]
The oxime ester photopolymerization initiator (E1) is preferably an oxime ester photopolymerization initiator represented by the following general formula (6).

一般式（６）において、Ｒ¹は、水素原子、または置換基を有しても良い、アルケニル基、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基、もしくはスルファモイル基であり、Ｒ₂は、水素原子、または置換基を有しても良い、アルケニル基、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基アシルオキシ基、もしくはアミノ基である。
Ｘは、直接結合又は−ＣＯ−基、Ｒ³は、置換基を有しても良いカルバゾール基を含む１価の有機基、Ｐｈ−Ｓ−Ｐｈ−基（Ｐｈは、置換基を有しても良い、フェニル基又はフェニレン基を示す）等であることが好ましい。 General formula (6):

In the general formula (6), R ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, An alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group, and R ₂ is hydrogen An alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, which may have an atom or a substituent, Arylsulfinyl group, alkylsulfonyl Group, an arylsulfonyl group, an acyloxy group, or an amino group.
X is a direct bond or —CO— group, R ³ is a monovalent organic group containing a carbazole group which may have a substituent, Ph—S—Ph— group (Ph has a substituent, Or a phenyl group or a phenylene group).

In the general formula (6), examples of the alkenyl group which may have a substituent in R ¹ include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. May have a plurality of carbon-carbon double bonds in the structure. Specific examples thereof include a 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, cyclopentadienyl group and the like, but are not limited thereto.

In the general formula (6), the alkyl group which may have a substituent in R ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 carbon atoms. To a linear, branched, monocyclic or condensed polycyclic alkyl group optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 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, isopropyl group, isobutyl group, isopentyl 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 and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. Examples thereof include, but are not limited to, CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _{2 and the} like.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

In the general formula (6), the alkyloxy group which may have a substituent in R ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or Examples thereof include linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

In the general formula (6), examples of the aryl group which may have a substituent in R ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms. Specific examples include a phenyl group, 1 -Naphthyl group, 2-naphthyl group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2 -Azulenyl group, 1-acenaphthyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5- Xylyl, mesityl, p-cumenyl, p-dodecylphenyl, p-cyclohexylphenyl, 4-biphenyl, o-fluorophenyl, m-chloropheny Group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like. However, it is not limited to these.

In the general formula (6), examples of the aryloxy group which may have a substituent for R ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group. 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group , 1-acenaphthyloxy group, 9-fluorenyloxy group and the like, but are not limited thereto.

In the general formula (6), the heterocyclic group which may have a substituent in R ¹ is an aromatic or aliphatic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Heterocyclic groups such as 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, Pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, Isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-ki Lydinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxanilyl, quinazolinyl, cinnolinyl, pteridinyl, 4aH-carbazolyl, 2-carbazolyl, 3-carbazolyl, β-carbolinyl, phenanthridine Group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, Pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group Thioxanthonyl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

In the general formula (6), the heterocyclic oxy group which may have a substituent for R ¹ is a monocyclic or condensed polyoxygen having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. A cyclic heterocyclic oxy group, and specific examples thereof include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyl. Examples thereof include, but are not limited to, an oxy group, a 2-carbazolyloxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group. .

In the general formula (6), examples of the alkylsulfanyl group which may have a substituent for R ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, Specific examples include, but are not limited to, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

In the general formula (6), examples of the arylsulfanyl group which may have a substituent in R ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms. Specific examples include a phenylthio group, Examples thereof include, but are not limited to, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and a 9-phenanthrylthio group.

In the general formula (6), the alkylsulfinyl group which may have a substituent in R ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. Specific examples thereof include a methylsulfinyl group, an ethylsulfinyl group, propyl Sulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, Examples thereof include, but are not limited to, a methyloxymethylsulfinyl group.

In the general formula (6), the arylsulfinyl group which may have a substituent in R ¹ is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfinyl group and a 1-naphthylsulfinyl group. 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylpheny A sulfinyl group, 4-phenylsulfanyl naphthoylmethyl Nils sulfinyl group, 4-dimethylamino-phenylsulfinyl but Le group and the like, but is not limited thereto.

In the general formula (6), the alkylsulfonyl group which may have a substituent in R ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, and propyl. Sulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, Examples thereof include, but are not limited to, methyloxymethylsulfonyl group.

In the general formula (6), the arylsulfonyl group which may have a substituent in R ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group. 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfuryl group § sulfonyl phenylsulfonyl group, 4-dimethylaminophenyl sulfonyl group, and the like, but not limited thereto.

In the general formula (6), the acyl group which may have a substituent in R ¹ is a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms. A bonded carbonyl group, a carbonyl group substituted by an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, a monocyclic or condensed group having 6 to 18 carbon atoms Examples include a carbonyl group substituted by a polycyclic aryloxy group, a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom are bonded. Specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myris Yl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxy Carbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group 9-anthrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4- Dimethylaminophenyloxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, Although a nicotinoyl group, an isonicotinoyl group, etc. can be mentioned, it is not limited to these.

In the general formula (6), examples of the acyloxy group which may have a substituent in R ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples thereof include an acetyloxy group, a propanoyloxy group, butane. Examples include a noyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphthylcarbonyloxy group.

In the general formula (6), the amino group which may have a substituent in R ¹ includes an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, and a benzylamino group. And dibenzylamino group.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

In the general formula (6), examples of the phosphinoyl group which may have a substituent in R ¹ include a phosphinoyl group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphinoyl group and diethylphosphinoyl group. Group, dipropylphosphinoyl group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, etc. Although it is mentioned, it is not limited to these.

In the general formula (6), examples of the carbamoyl group which may have a substituent in R ¹ include carbamoyl groups having 1 to 30 carbon atoms. Specific examples thereof include N-methylcarbamoyl group and N-ethylcarbamoyl group. Group, N-propylcarbamoyl group, N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N- 3-Nitrophenylcarbamoy Group, N-3-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N Examples include, but are not limited to, -methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

In the general formula (6), the sulfamoyl group which may have a substituent in R ¹ includes a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group and an N-alkylsulfamoyl group. N-arylsulfamoyl group, N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

In the general formula (6), an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an aryl which may have a substituent in R ² As a sulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, and an amino group, the alkenyl group that may have a substituent in the aforementioned R ¹ has a substituent. A good alkyl group, an alkyloxy group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a heterocyclic ring which may have a substituent Group, heterocyclic oxy group which may have a substituent, alkylsulfanyl group which may have a substituent, aryls which may have a substituent Rufanyl group, optionally substituted alkylsulfinyl group, optionally substituted arylsulfinyl group, optionally substituted alkylsulfonyl group, optionally substituted arylsulfonyl group These are synonymous with an acyloxy group which may have a substituent and an amino group which may have a substituent.

In the general formula (6), examples of these substituents in R ¹ and R ² include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, and alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group. Aryloxy groups such as phenoxy group and p-tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group, acetyl group and benzoyl group Group, isobutyryl group, acryloyl group, methacryloyl group, methoxalyl group and other acyl groups, methylsulfanyl group, tert-butylsulfanyl group and other alkylsulfanyl groups, phenylsulfanyl group, p-tolylsulfanyl group and other arylsulfani groups Group, alkylamino group such as methylamino group and cyclohexylamino group, dialkylamino group such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino group such as phenylamino group and p-tolylamino group, methyl group Alkyl group such as ethyl group, tert-butyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, phenyl group, p-tolyl group, xylyl Group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and other aryl groups, furyl group, thienyl group and other heterocyclic groups, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nito Group, a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, trimethyl ammonium Niu mill group, dimethylsulfoxide Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.
One or more of these substituents may be present, or one or more of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

  Among these oxime ester photopolymerization initiators (E1) represented by the general formula (6), the oxime ester photopolymerization initiator represented by the following general formula (7) or (8) is excellent in sensitivity. Is preferable.

[Oxime ester photopolymerization initiator represented by formula (7)]
General formula (7):

The general formula (7) corresponds to the case where X in the general formula (7) is a —CO— group and R ³ is a Ph—S—Ph— group, and R ^{4 to} R ⁶ represent a hydrogen atom or a substituent. An alkyl group or an aryl group which may be contained is preferable.

Further, in the general formula (7), an aryl group which may have a substituent as R ¹ is the alkyl group having 1 to 20 carbon atoms which may have a substituent as R ^2, R ⁴ ~ R ⁶ is preferably a hydrogen atom.

In the general formula (7), the alkyl group which may have a substituent or the aryl group which may have a substituent in R ^{4 to} R ⁶ includes an alkyl group or an aryl group in R ¹ and R ² Synonymous with group.

The alkyl group which may have a substituent or the substituent of the aryl group which may have a substituent has the same meaning as the substituent in R ¹ and R ² .

In the general formula (7), R ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent. The substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo group. A cycloalkyl group such as a heptyl group, a cyclooctyl group, or a cyclooctadecyl group;

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (7) include a photopolymerization initiator represented by the following chemical formula (7-1) or (7-2).
Chemical formulas (7-1) and (7-2):

[Carbazole group-containing oxime ester photopolymerization initiator represented by formula (8)]
General formula (8):

The general formula (8) corresponds to the case where R ³ in the general formula (6) is a monovalent organic group including a carbazole group which may have a substituent, and R ^{7 to} R ¹⁴ are R ¹ and R It is synonymous with the substituent in ² .

Further, in the general formula (8), an alkyl group having 1 to 20 carbon atoms which may have a substituent as R ¹ is of R ² as a substituted carbon atoms which may have a group 1 to 20 alkyl group, Alternatively, the aryl group which may have a substituent may be a hydrogen atom as R ^{9 to} R ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl which may have a substituent. Groups are preferred.

  When X in the general formula (8) is a direct bond, an oxime ester photopolymerization initiator represented by the following general formula (8a) is preferable.

[Carbazole group-containing oxime ester photopolymerization initiator represented by general formula (8a)]
General formula (8a):

The general formula (8a) corresponds to the case where X in the general formula (8) is a direct bond and R ³ is a monovalent organic group including a carbazole group which may have a substituent. R ^{7 to} R ¹⁰ and R ^{12 to} R ¹³ are preferably hydrogen atoms, and R ¹¹ is preferably an R ¹⁵ —CO— group or a nitro group. R ¹⁵ has the same meaning as the substituent in R ¹ and R ² , and is preferably an aryl group which may have a substituent. The R ¹⁵ —CO— group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, which may further have a substituent. More preferred is a benzoyl group or nitro group which may have a substituent.

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. Further, the alkyl group is preferably a methyl group or an ethyl group, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more —O— Monocyclic or condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic having 2 to 18 carbon atoms in R ¹ and optionally interrupted by one or more —O— Synonymous with alkyloxy group.

In the general formula (8a), R ² is preferably a C 1-20 alkyl group which may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo group. A cycloalkyl group such as a heptyl group, a cyclooctyl group, or a cyclooctadecyl group; Further, an aryl group which may have a substituent is preferable, and as the substituent, an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tert-butoxy group Etc. are preferred.

  Specific examples of the oxime ester photopolymerization initiator represented by the general formula (8a) include photopolymerization initiators represented by the following chemical formulas (8a-1) to (8a-4).

Chemical formulas (8a-1) to (8a-4):

[Keto-type carbazole group-containing oxime ester photopolymerization initiator represented by the general formula (8b)]
When X in the general formula (8) is a -CO- group, an oxime ester photopolymerization initiator represented by the following general formula (8b) is preferable.

General formula (8b):

The general formula (8b) corresponds to the case where X in the general formula (8) is a —CO— group and R ³ is a monovalent organic group including a carbazole group which may have a substituent. Is an oxime ester photopolymerization initiator.
R ^{7 to} R ¹⁰ and R ^{12 to} R ¹³ are preferably hydrogen atoms, and R ¹⁴ is preferably an aryl group which may have a substituent.
As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group is preferable, and a benzoyl group is more preferable.

  Specific examples of the oxime ester photopolymerization initiator having a keto-type carbazole group represented by the general formula (8b) include photopolymerization initiation represented by the following chemical formulas (8b-1) to (8b-4). Agents.

Chemical formulas (8b-1) to (8b-4):

  Commercially available products of these oxime ester photopolymerization initiators (E1) include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE) from BASF. OXE-01), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02) Yes. In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester compound.

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

<Antioxidant (F)>
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.

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

  Specific examples of the hindered phenol antioxidant include Yoshinox BHT (= 2,6-di-t-butyl-4-methylphenol), Tominox TT (= tetrakis- [methylene-3- (3,5 ′). -Di-t-butyl-4'-hydroxyphenyl) propionate] methane), Yoshinox SR, Yoshinox BB, Yoshinox 2246G, Yoshinox 425, Yoshinox 250, Yoshinox 930, Tominox SS, Tominox 917, GSY-314 (or more, Manufactured by API Corporation), IRGANOX245, IRGANOX259, IRGANOX565, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX107 , IRGANOX 1425WL, IRGANOX 1222, IRGANOX 1330 (above, manufactured by BASF Japan Ltd.), ADK STAB AO-70, ADK STAB AO-50, ADK STAB AO-330, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-80 (Asahi Denka) (Manufactured by Kogyo Co., Ltd.), Sumizer BM, Sumizer GM, Sumizer GP, Sumizer GS, Sumizer GA-80, Sumizer BP-101, Sumizer BP-76, and Sumizer BP-101 (manufactured by Sumitomo Chemical Co., Ltd.).

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.
In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

  Specific examples of the hindered amine-based antioxidant include Sanol LS-770, Sanol LS-765, Sanol LS-622LD, Kimasorp 944 (Sankyo Co., Ltd.), CYASORB UV-3346 (San Chemical Co., Ltd.), Knock rack 224, knock rack CD, Uvasil 299-299LM (above, Ouchi Shinsei Chemical Industry Co., Ltd.), MARK LA-63, MARKLA-68 (above, Asahi Denka Kogyo Co., Ltd.), TINUVIN 144, TINUVIN 312 (above, BASF・ Made by Japan).

  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 (3-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.

  Specific examples of phosphorus-based antioxidants include IRGAFOS168, IRGAFOS12, IRGAFOS38, IRGAFOSEPQ, (manufactured by BASF Japan Ltd.), Sumizer Z-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB PEP-4C, ADK STAB PEP-8F, ADK STAB PEP-8, ADK STAB PEP-45, ADK STAB PEP-11C, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB P, ADK STAB C, ADK STAB QL, ADK STAB 135A, ADK STAB 1178, ADK STAB 1500, ADK STAB 1500, ADK STAB 3010, ADK STAB 522A, ADK STAB TPP (above, manufactured by Asahi Denka Kogyo Co., Ltd.), GSY-202 (above, AP Aiko Ltd. poration), SANKOHCA (Sanko Co., Ltd.), JPH1200, JP302, JPM313, JP304, JP308, JPP100, JP333E, JP318E, JP312 (manufactured by API Corporation) and the like.

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

  Specific examples of sulfur-based antioxidants include IRGANOXPS800FD, IRGANOXPS802FD (above, manufactured by BASF Japan), Adekastab AO-503, Adekastab AO-412S (above, made by Asahi Denka Kogyo Co., Ltd.), Sumizer TPL-R, Sumizer TPM, TP Sumitizer TP-D, Sumitizer TL, Sumitizer MB (above, manufactured by Sumitomo Chemical Co., Ltd.), DLTP “Yoshitomi”, DSTP “Yoshitomi”, DMTP “Yoshitomi”, DTTP “Yoshitomi” (above, manufactured by API Corporation).

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

  Specific examples of the benzotriazole antioxidant include Tomisorp 600 (manufactured by Yoshitomi Fine Chemical), TINUVIN 326, TINUVIN 327, TINUVIN P, TINUVIN 328 (above, manufactured by BASF Japan Ltd.), VIOSORB583, VIOSORB590 (manufactured by Kyodo Yakuhin). .

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

  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-5 sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone, LA-51 (manufactured by Asahi Denka Kogyo Co., Ltd.) and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Specific examples of the benzophenone antioxidant include Tomisorp 800 (manufactured by API Corporation) and LA-51 (manufactured by Asahi Denka Kogyo Co., Ltd.).

  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.

  Specific examples of the triazine antioxidant include CYASORB UV-1164 (manufactured by Sun Chemical Co., Ltd.).

  Specifically, a compound such as IRGASTABFS042 (above, manufactured by BASF Japan Ltd.) can be used as the hydroxylamine-based antioxidant.

  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.

<Sensitizer (G)>
Further, the colored photosensitive composition of the present invention can contain a sensitizer (G).
Sensitizers (G) include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, and fluorene derivatives. , 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 Tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, Examples include, but are not limited to, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organic ruthenium 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 (G) may be used in any ratio as necessary. The blending amount when using the sensitizer (G) is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the total weight of the photopolymerization initiator (E) contained in the colored photosensitive composition. From the viewpoint of photocurability, the amount is more preferably 5 to 50 parts by weight.

<Binder resin>
The binder resin is a colorant such as a pigment or a dye, in particular, one that disperses the dye monomer (A1) of the present invention, or a dye that penetrates the dye monomer (A1) 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 photosensitive coloring composition for a color filter, it is adsorbed from the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and the dye monomer (A1) of the present invention. The dispersion of the pigment and the dye monomer of the present invention (A1) depends on the balance of the carboxyl group that functions as an alkali-soluble group during development and the aliphatic group and aromatic group that functions as an affinity group for the colorant carrier and solvent. The resin having an acid value of 20 to 300 mgKOH / g is preferably used. 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 parts by weight or more based on 100 parts 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 parts by weight or less.

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

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

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (A1) and (b).

[Method (A1)]
As the method (A1), 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 (A1), 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 (A1) 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 it is set as 2 or more types of mixed solvents, it is preferable that said preferable organic solvent is contained 65 to 95 weight% in 100 weight part of the whole organic solvent. In particular, propylene glycol monomethyl ether acetate is preferably the main component, and preferably 65 to 100% by weight in all organic solvents.

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

<Method for producing colored composition>
The coloring composition for a color filter of the present invention comprises a colorant carrier comprising the above-mentioned resin and, if necessary, a solvent, a colorant comprising the dye monomer (A1) of the present invention and a specific organic pigment (B). In particular, it can be produced by being finely dispersed using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor together with a dispersion aid such as a pigment derivative. In addition, when the solubility of the dye monomer (A1) of the present invention is high, specifically, the solubility in a solvent to be used is high. There is no need to manufacture it in a dispersed manner.

  In addition, the coloring composition for a color filter of the present invention is obtained by separately dispersing a pigment, the dye monomer (A1) of the present invention, a specific organic pigment (B), and other colorants in a colorant carrier. Can also be produced.

[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 great effect of preventing reaggregation of the colorant after dispersion. When used, a color filter having a high spectral transmittance can be obtained.

  In the present invention, the dye monomer (A1) 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 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts 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 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts 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, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, 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 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

  The colored composition for a color filter of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer (D) and / or a photopolymerization initiator (E).

  In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a solvent developing type or an alkali developing type coloring. It can be adjusted in the form of a resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the colorant, and 10 to 150 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

  Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.

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

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

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

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

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

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

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

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

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

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

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part 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 parts by weight with respect to 100 parts 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 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the colorant in the coloring composition.

<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. “PGMAC” means propylene glycol monomethyl ether acetate.

(Resin polymerization average molecular weight (Mw))
The polymerization average molecular weight (Mw) of the resin is a polystyrene equivalent measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector 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) 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.

  Subsequently, a method for producing dye monomers, other pigments, and a binder resin used in Examples and Comparative Examples, a method for preparing a resin-type dispersant solution, and a method for producing a pigment dispersion and a photosensitive coloring composition And will be described.

<Binder resin production method>
(Adjustment of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) 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. Acrylic resin solution 1 was prepared by adding ether acetate.

<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%.

BV10: C.I. I. Basic violet 10

<Production Method of Coloring Composition for Color Filter (Dye Monomer / Dispersion Solution)>
(Production Method of Dye Monomer / Dispersion Solution S-1)
After mixing various materials according to the following, the dye monomer / dispersion solution S-1 was obtained by performing ultrasonic irradiation for 1 hour.
Dye monomer / ST-1: 4.0 parts Acrylic resin solution (B1-1): 30.0 parts Cyclohexanone: 16.0 parts Total: 50.0 parts

(Production Method of Dye Monomer / Dispersion Solution S-2 to 15)
In the case of the dye monomer / dispersion solution (S-1), except that the dye monomer ST-1 in the method for producing the dye monomer / dispersion solution (S-1) is changed to the material described in Table 2 In the same manner as above, Dye monomer / dispersion solutions S-2 to 15 were obtained.

<Method for producing diketopyrrolopyrrole pigment (B1)>
[Diketopyrrolopyrrole Pigment (b1) Represented by Formula (4)]
(Diketopyrrolopyrrole pigment (b1-1))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was redispersed in 3500 parts of methanol cooled to 0 ° C. to obtain a suspension having a methanol concentration of about 90%, and stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the diketopyrrolopyrrole compound aqueous paste obtained by filtering with an ultrafiltration machine was dried at 80 ° C. for 24 hours and pulverized, whereby the brominated diketo represented by the formula (4) was obtained. 150.8 parts of pyrrolopyrrole pigment were obtained.

  Subsequently, a salt milling process was performed. 100 parts of brominated diketopyrrolopyrrole pigment represented by formula (4), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 60 ° C. for 6 hours. Salt milling was performed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of diketopyrrolopyrrole pigment (b1-1) were obtained.

[Diketopyrrolopyrrole Pigment (b2) Represented by General Formula (5)]
(Diketopyrrolopyrrole pigment (b2-1))
While adding 220 parts of tert-amyl alcohol to the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added and heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 85.0 parts of the compound of the following formula (9) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in the reaction vessel 2. This was dissolved and added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, filtering off and washing with methanol, the specific heterodiketo represented by the formula (5-1a) 88.1 parts of pyrrolopyrrole pigment were obtained.

Formula (9):

  Subsequently, a salt milling process was performed. 200 parts of the specific hetero diketopyrrolopyrrole pigment represented by the formula (5-1a), 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 put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a diketopyrrolopyrrole pigment (b2-1) was obtained.

(Diketopyrrolopyrrole pigment (b2-2))
Except for changing 60.9 parts of 4-cyanobiphenyl to 54.1 parts of 4-tert-butylbenzonitrile, in the same manner as in the method for producing the specific heterodiketopyrrolopyrrole pigment represented by the formula (5-1a), 83.9 parts of specific hetero diketopyrrolopyrrole pigments represented by the formula (5-2a) were obtained.
The specific hetero diketopyrrolopyrrole pigment represented by the formula (5-2a) thus obtained is subjected to the same salt milling method as that of the diketopyrrolopyrrole pigment (b2-1), and the diketopyrrolopyrrole pigment (b2-2). Got.

(Diketopyrrolopyrrole pigment (b2-6))
Same as the method for producing the specific heterodiketopyrrolopyrrole pigment represented by the formula (5-1a) except that 60.9 parts of 4-cyanobiphenyl is changed to 87.8 parts of N, N-dibutyl-3-cyanobenzamide. Thus, 83.8 parts of the specific hetero diketopyrrolopyrrole pigment represented by the formula (5-4b) was obtained.
The specific hetero diketopyrrolopyrrole pigment represented by the formula (5-4b) thus obtained is subjected to the same salt milling method as that of the diketopyrrolopyrrole pigment (b2-1), and the diketopyrrolopyrrole pigment (b2-6). Got.

(Diketopyrrolopyrrole pigment (b2-9))
While adding 220 parts of tert-amyl alcohol to the reaction vessel 1 and cooling with a water bath, 32 parts of 60% NaH was added and heated and stirred at 90 ° C. Next, 100 parts of tert-amyl alcohol, 99.2 parts of the compound of the following formula (10) synthesized by the method of Tetrahedron, 58 (2002) 5547-5565, and 60.9 parts of 4-cyanobiphenyl are heated in the reaction vessel 2. This was dissolved and added dropwise to the reaction vessel 1 over 2 hours. After reacting at 120 ° C. for 10 hours, cooling to 60 ° C., adding 400 parts of methanol and 50 parts of acetic acid, filtering off and washing with methanol, the specific heterodiketo represented by the formula (5-19) 87.8 parts of pyrrolopyrrole pigment were obtained.

Formula (10):

  The specific hetero diketopyrrolopyrrole pigment represented by the formula (5-19) thus obtained was subjected to the same salt milling method as that of the diketopyrrolopyrrole pigment (b2-1), and the diketopyrrolopyrrole pigment (b2-9). Got.

[Other diketopyrrolopyrrole pigments]
(Diketopyrrolopyrrole pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. Pigment Red 254 (BASF “B-CF”) 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. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a refined diketopyrrolopyrrole pigment (PR254-1) was obtained.

<Method for producing azo pigment>
(Azo red pigment (PR166-1))
Disazo red pigment C.I. I. 200 parts of Pigment Red 166 (“Irga Fore Red Scarlet RN” manufactured by BASF), 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 put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A disazo-based fine red pigment (PR166-1) was obtained.

(Azo-based red pigment (PR221-1))
Disazo red pigment C.I. I. 200 parts of Pigment Red 221 (“Chromophthal Red 2B” manufactured by BASF), 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 put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A disazo-based fine red pigment (PR221-1) was obtained.

(Azo-based red pigment (PR242-1))
Disazo red pigment C.I. I. 200 parts of Pigment Red 242 (Clariant's “Sandorinscarlet 4RF”), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A disazo-based fine red pigment (PR242-1) was obtained.

(Azo-based orange pigment (PO38-1))
Naphthol AS orange pigment C.I. I. Pigment Orange 38 (Clariant “NOVOPERM RED HFG”) 100 parts, sodium chloride 1200 parts, and diethylene glycol 120 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and salt milling Processed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A refined orange pigment (PO38-1) was obtained.

<Manufacturing method of other fine pigments>
(Production of refined PR177 pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 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 put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Anthraquinone-based fine red pigment (PR177-1) was obtained.

(Miniaturized yellow pigment (PY 139-1))
Azo-based yellow pigments C.I. I. 500 parts of Pigment Yellow 139 ("Irgafore Yellow 2R-CF" manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, an azo-based fine yellow pigment (PY139-1) was obtained.

(Miniaturized yellow pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 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. A nickel complex-based fine yellow pigment (PY150-1) was obtained.

(Miniaturized yellow pigment (PY185-1))
Isoindoline yellow pigment C.I. I. 500 parts of Pigment Yellow 185 (“Pariol Yellow D1155” manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, an isoindoline-based fine yellow pigment (PY185-1) was obtained.

(Miniaturized green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 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 put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based fine green pigment (PG58-1) was obtained.

(Miniaturized blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “LIONOL BLUE ES”, specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A phthalocyanine-based fine blue pigment (PB15: 6-1) was obtained.

(Miniaturized purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” 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 put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A dioxazine-based purple refined purple pigment (PV23-1) 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 40% by weight non-volatile solution and used as the resin type dispersant solution 1.

<Method for producing pigment dispersion>
(Pigment dispersion (P-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (P-1) whose non-volatile component is 20 weight% was produced.
Refined organic pigment PR254-1: 11.0 parts Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution 1: 5.0 parts

(Pigment dispersion (P-2 to 17))
A pigment dispersion (P-2 to 17) was produced in the same manner as the pigment dispersion (P-1) except that the type of pigment was changed as shown in Table 3.

<Production of Color Filter Coloring Composition (Photosensitive Coloring Composition)>
[Example 1]
(Red photosensitive coloring composition (R-1))
The following mixture (100 parts in total) was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a red photosensitive coloring composition (R-1).
(Dye dispersion) (50 parts in total)
Dye monomer dispersion solution (S-1): 13.5 parts Pigment dispersion (P-1): 36.5 parts Acrylic resin solution 1: 15.0 parts Photopolymerizable monomer (manufactured by Toagosei Co., Ltd. Aronix M-402 "): 2.0 parts Dipentaerythritol hexaacrylate photopolymerization initiator (E1-3) (" OXE-02 "manufactured by BASF): 1.0 part Etanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-
Carbazol-3-yl]-, 1- (0-acetyloxime)
Methoxypropyl acetate: 32.0 parts

[Examples 2-45, Comparative Examples 1-3]
(Red photosensitive coloring composition (R-2 to 48)
The red photosensitive coloring composition (R-2 to 48) was changed in the same manner as the red photosensitive coloring composition (R-1) except that the pigment dispersion was changed to the type and blending amount of the pigment dispersion shown in Table 4. Obtained. In each photosensitive coloring composition adjustment, it added so that the sum total of a pigment dispersion might be 50 parts, and prepared 100 parts of red photosensitive coloring compositions.

The abbreviations in Table 4 are described below.
<< Photopolymerization initiator >>
Photopolymerization initiator (E1-1): Chemical formula (7-1), non-carbazole type oxime ester initiator (“IRGACURE OXE-01” manufactured by BASF: 1,2-octanedione, 1
-[4- (phenylthio) phenyl-, 2- (O-benzoyloxime)])
Photopolymerization initiator (E1-2): chemical formula (7-2), non-carbazole type oxime ester initiator chemical formula (7-2):

Oxime ester photopolymerization initiator (E1-3): Chemical formula (8a-1), carbazole group-containing oxime ester initiator ("IRGACURE OXE 02" manufactured by BASF: Etanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-
Acetyl oxime))

Photopolymerization initiator (E1-4): chemical formula (8a-2), carbazole group-containing oxime ester initiator chemical formula (8a-2):

Photopolymerization initiator (E1-5): Chemical formula (8b-1), keto-type carbazole group-containing oxime ester initiator chemical formula (8b-1):

Photopolymerization initiator (E1-6): chemical formula (8b-2), keto-type carbazole group-containing oxime ester initiator chemical formula (8b-2):

Photopolymerization initiator (E1-7): chemical formula (8b-3), keto-type carbazole group-containing oxime ester initiator chemical formula (8b-3):

Photopolymerization initiator (E1-8): chemical formula (8b-4), keto-type carbazole group-containing oxime ester initiator chemical formula (8b-4):

Photopolymerization initiator (E2-1): non-oxime ester initiator (“IRGACURE 379” manufactured by BASF: 2- (dimethylamino) -2-[(4-
Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone)
Photopolymerization initiator (E2-2): non-oxime ester initiator (“IRGACURE 907” manufactured by BASF: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one)

Antioxidant A: Hindered phenol antioxidant (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Antioxidant B: sulfur-based antioxidant 3,3′-thiodipropanoic acid dioctadecyl antioxidant C: phosphorus-based antioxidant tris [2,4-di- (tert) -butylphenyl] phosphine antioxidant D: Hindered amine antioxidant bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate antioxidant E: salicylate antioxidant p-octylphenyl salicylate PGMAC: propylene glycol monomethyl ether acetate

<Evaluation of Color Filter Coloring Composition (Photosensitive Coloring Composition)>
Using the obtained colored composition for color filter (R1 to 48), evaluation of color characteristics (brightness), contrast ratio (CR) of the coating film, and heat resistance were performed by the following methods. Table 5 shows the evaluation results.
(Evaluation of color characteristics (lightness))
The obtained red photosensitive coloring composition is coated on a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes. 658, y = 0.325 was obtained. 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.
◎ ... 19.3 or more ○ ... 19.1 or more and less than 19.3 △ ... 18.9 or more and less than 19.1 × ... less than 18.9

(Evaluation of contrast ratio (CR) of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

The obtained red photosensitive coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 220 ° C. for 60 minutes. The coating film substrate was produced by allowing to cool. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to a chromaticity of x = 0.620 with a C light source after heat treatment at 220 ° C. The contrast ratio was determined according to the following criteria.
◎: 7000 or more ○: 6000 or more and less than 7000 Δ: 5000 or more and less than 6000 ×: less than 5000

(Evaluation of heat resistance of coating film)
The obtained red photosensitive coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 220 ° C. for 60 minutes. The coating film substrate was produced by allowing to cool. The prepared coating film substrate was adjusted to have a coating film thickness of 1.5 μm after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
A: ΔEab * is less than 3.0 ○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 X: ΔEab * is 10.0 or more

(Sensitivity evaluation)
After coating the obtained red photosensitive coloring composition on a 10 cm × 10 cm glass substrate by spin coating, the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven to obtain a coating film of about 2 μm. It was. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 30 minutes in a clean oven. The pattern film thickness in the 100 μm photomask portion of the filter segment formed by the above method was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
The rank of evaluation is as follows.
○: Less than 50 mJ / cm ² Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² ×: 100 mJ / cm ² or more

  From Table 5, the coloring composition using the pigment monomer (A1) represented by the general formula (1) and the specific pigment (B) has lightness and heat resistance as compared with the coloring composition of the comparative example. Or both were high results.

<Manufacture of color filters>
(Green photosensitive coloring composition (G-1))
A mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (G-1).
Pigment dispersion (P-15): 32.0 parts Pigment dispersion (P-13): 18.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ("Aronix M-" manufactured by Toagosei Co., Ltd.) 402 "): 2.0 parts dipentaerythritol hexaacrylate photopolymerization initiator (" OXE-02 "manufactured by BASF): 1.5 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-
Carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (B-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition (B-1).
Pigment dispersion (P-16): 45.0 parts Pigment dispersion (P-14): 5.0 parts Acrylic resin solution 1: 7.5 parts Photopolymerizable monomer ("Aronix M-" manufactured by Toagosei Co., Ltd.) 402 "): 2.0 parts photopolymerization initiator (" OXE-02 "manufactured by BASF): 1.5 parts cyclohexanone: 39.0 parts

[Example 46]
The red photosensitive coloring composition (R-1) of the present invention was applied to a glass substrate on which a black matrix was previously formed by spin coating, and then prebaked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp.
Thereafter, the substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (G-1) is used, the green coloring pixel layer is formed in the same manner as the red coloring pixel layer, and further the blue photosensitive coloring composition (B-1) is used. A blue colored pixel layer was formed to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

[Examples 46 to 49, Comparative Example 4]
Except having changed into the red photosensitive coloring composition shown in Table 6, the color filter (CF-2-5) was obtained like the color filter (CF-1).

<Evaluation of color filter>
(Brightness (spectral transmittance))
The brightness of the produced color filter was measured. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). The results are shown in Table 6.

  The color filter using the red coloring composition of the present invention was a result of high brightness, and the effect of the present invention was proved.

Claims (14)

A color filter coloring composition containing a colorant, a resin, and a solvent, wherein the colorant comprises a dye monomer (A1) represented by the following general formula (1) and an organic pigment (B) The organic pigment (B) contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment (B1) and an azo pigment (B2). Composition.
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—) and 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 organic dye skeleton Q in the general formula (1) is a xanthene skeleton represented by the general formula (2), an anthraquinone skeleton represented by the general formula (3-1), and an anthraquinone system represented by the general formula (3-2). The coloring composition for a color filter according to claim 1, which is at least one organic dye skeleton selected from the group consisting of a skeleton and an anthraquinone skeleton represented by the general formula (3-3).
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), (3-2), (3-3):

[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. ] The diketopyrrolopyrrole pigment (B1) is selected from the group consisting of a diketopyrrolopyrrole pigment (b1) represented by the following general formula (4) and a diketopyrrolopyrrole pigment (b2) represented by the following general formula (5). The coloring composition for a color filter according to claim 1 or 2, comprising at least one selected.
General formula (4), (5):

[In General Formula (5), X represents a chlorine atom or a bromine atom, and B and D are each independently a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, An optionally substituted phenyl group, —CF ₃ , —OR ¹³ , —SR ¹⁴ , —N (R ¹⁵ ) R ¹⁶ , —COOR ¹⁷ , —CONH ₂ , —CONHR ¹⁸ , —CON (R ¹⁹ ) R ²⁰ , —SO ₂ NH ₂ , —SO ₂ NHR ²¹ , or —SO ₂ N (R ²² ) R ²³ , wherein R ^{13 to} R ²³ are each independently an alkyl group having 1 to 12 carbon atoms. A phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, B and D do not become hydrogen atoms at the same time. ] The diketopyrrolopyrrole pigment (b2) represented by the general formula (5) is represented by the following general formula (5-1), the following general formula (5-2), the following general formula (5-3), or the following general formula ( The colored composition for a color filter according to claim 3, which is any one of 5-4).
Formulas (5-1) to (5-4):

[In the general formulas (5-1 to 5-4), X represents a chlorine atom or a bromine atom, and R ^{24 to} R ²⁶ each independently represents an alkyl group having 1 to 12 carbon atoms or a substituent. It is a phenyl group which may have. ]   The diketopyrrolopyrrole pigment (B1) is C.I. I. Pigment Red 254 is contained, The coloring composition for color filters of any one of Claims 1-4 characterized by the above-mentioned. The diketopyrrolopyrrole pigment (B1) contains the diketopyrrolopyrrole pigment (b2) represented by the general formula (5) and contains the diketopyrrolopyrrole pigment (b2) represented by the general formula (5) The amount is 1 to 15% by weight in 100% by weight of the diketopyrrolopyrrole pigment (B1), and the coloring composition for a color filter according to any one of claims 1 to 5.
General formula (5):

  The azo pigment (B2) is C.I. I. Pigment red 166, C.I. I. Pigment red 221, C.I. I. Pigment red 242, and C.I. I. The coloring composition for a color filter according to any one of claims 1 to 6, wherein the coloring composition is at least one selected from the group consisting of CI Pigment Orange 38.   The colored composition for a color filter according to any one of claims 1 to 7, further comprising a photopolymerizable monomer (D) and / or a photopolymerization initiator (E).   The colored composition for a color filter according to claim 8, wherein the photopolymerization initiator (E) contains an oxime ester photopolymerization initiator (E1).   The colored composition for a color filter according to claim 9, wherein the oxime ester photopolymerization initiator (E1) has a carbazole group.   Furthermore, antioxidant (F) is contained, The coloring composition for color filters of any one of Claims 1-10 characterized by the above-mentioned.   The antioxidant (F) is at least one antioxidant selected from the group of hindered phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. The coloring composition for a color filter according to claim 11.   The color filter according to claim 11 or 12, wherein the content of the antioxidant (F) is 0.5 to 5.0 wt% based on the solid content weight of the color filter coloring composition. Coloring composition.   A color filter comprising at least a red filter segment, a green filter segment, and a blue filter segment, wherein at least one filter segment is formed by the color filter coloring composition according to any one of claims 1 to 13. filter.