JP2019020635A - Colorant for color filter, coloring composition for color filter, and color filter - Google Patents

Abstract

To provide a colorant for a color filter, which allows manufacturing of a color filter having high lightness and a high contrast ratio, to provide a color filter having high lightness and a high contrast ratio formed by using the above colorant for a color filter, and to provide a colorant for a color filter, which excels in hue properties when used as a colorant.SOLUTION: A coloring composition for a color filter comprising a colorant, a resin and a solvent is provided, in which the colorant comprises a specific xanthene dye (A1) represented by general formula (1) and a xanthene dye (A2) having fluorescence.SELECTED DRAWING: None

Description

  The present invention includes a color liquid crystal display device, a color filter colorant used in the production of a color filter used for a color image pickup tube element, a color filter color composition, and a filter segment formed using these. The present invention relates to a color filter.

  In color filter applications, attention has been focused on dye-based color materials in order to achieve a high contrast ratio and high brightness that cannot be achieved with pigments. Of these, xanthene dyes such as rhodamine dyes and eosin dyes are expected to be materials that achieve high brightness because of their superior color characteristics.

  On the other hand, since the xanthene dye emits fluorescence, there is a problem that the contrast ratio is lowered. Patent Documents 1 to 3 describe that a xanthene dye and a compound having fluorescence quenching ability are used in combination, but in order to meet the higher demanded quality (high brightness and high contrast ratio) in recent years. In some cases, it was insufficient.

  As described above, a color filter capable of achieving both high brightness and high contrast ratio using a xanthene dye has not been realized.

JP 2012-194523 A JP2013-101166A JP 2014-215515 A

  The objective of this invention is providing the coloring composition for color filters which enables preparation of the color filter which has high brightness and a high contrast ratio. Moreover, the objective of this invention is providing the color filter of the high brightness and high contrast ratio which uses the said coloring composition for color filters. Furthermore, an object of the present invention is to provide a color filter colorant having little fluorescence and having excellent color characteristics when used as a colorant.

  As a result of intensive studies to solve the above problems, the present inventor has obtained a coloring composition for a color filter comprising a specific xanthene dye (A1) having a benzimidazolone group and a xanthene dye (A2) having fluorescence. The present inventors have found that the reduction in contrast ratio can be improved by the fluorescence quenching effect of the xanthene dye (A1) and that high brightness and high contrast ratio can be achieved, and the present invention has been made based on this finding.

  That is, the present invention is a color filter coloring composition containing a colorant, a resin, and a solvent, wherein the colorant is a xanthene dye (A1) represented by the following general formula (1) and xanthene having fluorescence. It is related with the coloring composition for color filters containing a pigment | dye (A2).

General formula (1)

[In General Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Y ₁ is an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent, and 6 carbon atoms which may have a substituent. 10 to 10 aryl groups or a group represented by the general formula (2). R ₂ and Y ₁ may together form a ring containing a nitrogen atom. T ₁ and T ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₁ is a hydrogen atom, a methyl group or a methoxy group. When the general formula (1) has an acidic group, the acidic group may be salted with a resin Z ⁺ having a cationic group in the side chain. ]

General formula (2)

[In General Formula (2), T ₃ and T ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₂ is a hydrogen atom, a methyl group or a methoxy group. * Represents a linking site. When the general formula (2) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ]

Moreover, this invention relates to the said coloring composition for color filters whose xanthene dye (A1) is the xanthene dye (A1 ') represented by following General formula (3).
General formula (3)

[In General Formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Y ₂ is an alkyl group having 1 to 10 carbon atoms that may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms that may have a substituent, or 6 carbon atoms that may have a substituent. Represents 10 to 10 aryl groups. R ₄ and Y ₂ may together form a ring containing a nitrogen atom. T ₅ and T ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₃ is a hydrogen atom, a methyl group or a methoxy group. When the general formula (3) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ]

  In the present invention, the content of the xanthene dye (A1) is 0.1% by mass to 10% with respect to the total of the xanthene dye (A1) represented by the general formula (1) and the xanthene dye (A2) having fluorescence. It is related with the said coloring composition for color filters which is 0 mass%.

The present invention also relates to the colored composition for a color filter, wherein the xanthene dye (A1) represented by the general formula (1) is a salt-forming compound with a resin Z ⁺ having a cationic group in the side chain.

The present invention also relates to the above color filter coloring composition, wherein the fluorescent xanthene dye (A2) is a salt-forming compound of xanthene acidic dye and a resin Z ⁺ having a cationic group in the side chain.

  Moreover, this invention relates to the said coloring composition for color filters in which a coloring agent contains an organic pigment further.

  Moreover, this invention relates to the said coloring composition for color filters which contains at least one of a photopolymerizable monomer and a photoinitiator further.

  Moreover, this invention relates to the color filter formed with the said coloring composition for color filters.

Furthermore, this invention relates to the colorant for color filters containing the xanthene pigment | dye (A1 ') represented by following General formula (3).
General formula (3)

[In General Formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. T ₅ and T ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Y ₂ is an alkyl group having 1 to 10 carbon atoms that may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms that may have a substituent, or 6 carbon atoms that may have a substituent. Represents 10 to 10 aryl groups. R ₄ and Y ₂ may together form a ring containing a nitrogen atom. W ₃ is a hydrogen atom, a methyl group or a methoxy group. When the general formula (3) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ]

  According to the present invention, a coloring composition for a color filter that improves the reduction in contrast ratio, which has been a problem when using a xanthene dye, and enables the production of a color filter that achieves both high brightness and high contrast ratio, A color filter using the color filter coloring composition and a color filter colorant having little color emission and excellent color characteristics when used as a colorant can be provided.

  The color composition for a color filter of the present invention includes a colorant containing a xanthene dye (A1) represented by the general formula (1) and a xanthene dye (A2) having fluorescence, a resin, and a solvent. Coloring composition. Hereinafter, various components of the coloring composition for a color filter of the present invention will be described. In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ". Further, “CI” mentioned in the present specification means a color index (CI).

<Colorant>
The coloring composition for a color filter of the present invention includes a xanthene dye (A1) represented by the general formula (1) and a fluorescent xanthene dye (A2) as a colorant, thereby achieving both high brightness and high contrast ratio. Can be achieved. Further, as will be described later, it is also preferable to use an organic pigment in combination because the chromaticity can be easily adjusted and the resistance can be improved.

<Xanthene Dye (A1) Represented by General Formula (1)>
The xanthene dye (A1) represented by the general formula (1) will be described.

General formula (1)

[In General Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Y ₁ is an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent, and 6 carbon atoms which may have a substituent. 10 to 10 aryl groups or a group represented by the general formula (2). R ₂ and Y ₁ may together form a ring containing a nitrogen atom. T ₁ and T ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₁ is a hydrogen atom, a methyl group or a methoxy group. When the general formula (1) has an acidic group, the acidic group may be salted with a resin Z ⁺ having a cationic group in the side chain. ]

General formula (2)

[In General Formula (2), T ₃ and T ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₂ is a hydrogen atom, a methyl group or a methoxy group. * Represents a linking site. When the general formula (2) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ]

Examples of the alkyl group having 1 to 10 carbon atoms in R ₁ and R ₂ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, n-hexyl group, n-octyl group, 2 -In addition to linear or branched alkyl groups such as ethylhexyl group, trifluoromethyl group, 2-ethoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group , 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group, alkoxyl group such as methoxy group, alkyl group having 1 to 10 carbon atoms having a substituent such as hydroxy group and sulfo group. .

An alkyl group having 1 to 10 carbon atoms which may have a substituent in Y ₁ has the same meaning as the alkyl group having 1 to 10 carbon atoms in _{R 1} and _{R 2.}

Examples of the cycloalkyl group having 5 to 8 carbon atoms that may have a substituent for Y ₁ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. An unsubstituted C5-C8 cycloalkyl group is preferable and a cyclohexyl group is more preferable.

Examples of the aryl group having 6 to 10 carbon atoms which may have a substituent in Y ₁ include an aryl group such as a phenyl group and a naphthyl group, a p-methylphenyl group, a p-bromophenyl group, and p-nitrophenyl. Group, p-methoxyphenyl group, 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,6-dimethoxyphenyl group, 4-bromo-2,6-dimethylphenyl group, 4-sulfo- 2,6-dimethylphenyl group, 2-methoxy-5-sulfophenyl group and the like can be mentioned. Among these, a phenyl group substituted with a methyl group, a methoxy group, a sulfo group, or a bromo group is preferable, and a 2,6-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,6-dimethoxyphenyl group, 4- A bromo-2,6-dimethylphenyl group, a 4-sulfo-2,6-dimethylphenyl group, and a 2-methoxy-5-sulfophenyl group are more preferable.

Alkyl group having 1 to 10 carbon atoms in T ₁ through T ₄ has the same meaning as alkyl group having 1 to 10 carbon atoms in _{R 1} and _{R 2.}

In addition, the alkyl group having 1 to 10 carbon atoms, the cycloalkyl group having 5 to 8 carbon atoms, and the aryl group having 6 to 10 carbon atoms are substituted with —SO ₃ H; —COOH; and 1 of these acidic groups. value to trivalent metal salt or alkyl ammonium salt, -SO ₃ ^- Z ^+, or CO ₂ ^- Z ⁺ may have. Z ⁺ represents a resin having a cationic group in the side chain.

  Examples of monovalent to trivalent metal salts of acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Examples of the alkyl ammonium salt of acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. Of the quaternary alkyl ammonium salts. The resin having a cationic group in the side chain has the same meaning as described below.

Examples of the case where R ₂ and Y ₁ together form a ring containing a nitrogen atom include the following.

When R ₂ and Y ₁ together form a ring containing a nitrogen atom, the formed ring may have a substituent. Examples of the substituent include a methyl group, an ethyl group, a chlorine atom, —COOH, —OH, —SO ₃ H and the like. —COOH, —OH, —SO ₃ H is a resin having a cationic group in the side chain. It may be salted with. Further, the ring may contain an oxygen atom, a nitrogen atom or the like. Among them, it is preferable that R ₂ and Y ₁ together form a 6-membered ring containing a nitrogen atom.

As R ₁ and R ₂ , an unsubstituted or sulfo group having 1 to 10 carbon atoms is preferable, an unsubstituted alkyl group having 1 to 5 carbon atoms is more preferable, and a propyl group is particularly preferable. T ₁ and T ₂ are preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a propyl group, or a butyl group. Y ₁ is preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent or an aryl group having 6 to 10 carbon atoms which may have a substituent, and carbon which may have a substituent. An aryl group having a number of 6 to 10 is more preferable, and a phenyl group substituted with a methyl group, a methoxy group, a sulfo group, or a bromo group is more preferable. Among them, 2,6-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2,6-dimethoxyphenyl group, 4-bromo-2,6-dimethylphenyl group, 2-methoxy-5-sulfophenyl group, A phenyl group substituted with a sulfo group is preferred. Moreover, when it has an acidic group as a substituent, it is preferably a salt-forming compound with a resin Z ⁺ having a cationic group in the side chain, and the acidic group is preferably a sulfo group. As W ₁ and W ₂ , a hydrogen atom is preferable.

[Xanthene dye (A1 ′)]
As the xanthene dye (A1), a xanthene dye (A1 ′) represented by the following general formula (3) is preferable. Further, the xanthene dye (A1 ′) can be used as a colorant for a color filter.

General formula (3)

[In general formula (3),
R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms that may have a substituent.
Y ₂ is an alkyl group having 1 to 10 carbon atoms that may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms that may have a substituent, or 6 carbon atoms that may have a substituent. Represents 10 to 10 aryl groups.
R ₄ and Y ₂ may together form a ring containing a nitrogen atom.
T ₅ and T ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
W ₃ is a hydrogen atom, a methyl group or a methoxy group.
When the general formula (3) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ]

In General Formula (3), the alkyl group having 1 to 10 carbon atoms that may have a substituent, the cycloalkyl group having 5 to 8 carbon atoms that may have a substituent, and the substituent may be included. The resin Z ⁺ having a C 6-10 aryl group, a ring containing a nitrogen atom, and a cationic group in the side chain has the same meaning as described in the general formulas (1) and (2).

[Resin Z ⁺ having a cationic group in the side chain]
The resin Z ⁺ having a cationic group in the side chain is not particularly limited as long as it has at least one onium base in the side chain, but a preferable onium salt structure is from the viewpoint of availability and the like. , Ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and in view of storage stability (thermal stability), ammonium salts, iodonium salts, and sulfonium salts are more preferable. More preferred is an ammonium salt. The xanthene dye (A1) represented by the general formula (1) and the fluorescent xanthene dye (A2) are preferably salt-forming compounds with a resin Z ⁺ having a cationic group in the side chain.

(Acrylic resin containing a structural unit represented by the general formula (4))
The resin Z ⁺ having a cationic group in the side chain is desirably the same type as the resin constituting the color filter coloring composition. Since an acrylic resin is preferably used as the resin, Z ⁺ is preferably an acrylic resin, and more preferably an acrylic resin containing a structural unit represented by the following general formula (4).

General formula (4)

[In General Formula (4), R ₂₁ represents a hydrogen atom or an alkyl group which may have a substituent. R _{22 to} R ₂₄ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, Two of R _{22 to} R ₂₄ may be bonded to each other to form a ring. Q is an alkylene group, an arylene _{group, -CONH-R 25 -, -} COO-R 25 - _{represents, R 25} represents an alkylene group. V ⁻ represents an inorganic or organic anion. ]

Examples of the alkyl group for R ₂₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable. When the alkyl group represented by R ₂₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among the above, R ₂₁ is most preferably a hydrogen atom or a methyl group.

Examples of the alkyl group in R _{22 to} R ₂₄ include a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethyl Butyl), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R _{22 to} R ₂₄ include linear or branched alkenyl groups (allyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl). And a cycloalkenyl group (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R _{22 to} R ₂₄ include a monocyclic aryl group (phenyl, tolyl, xylyl, etc.), a condensed polycyclic aryl group (naphthyl, anthryl, phenanthryl, anthraquinolyl, fluorenyl, naphthoquinolyl, etc.) and aromatic. Heterocyclic hydrocarbon groups (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxan Tenyl (a group derived from xanthone) and 9-oxothioxanthenyl (a group derived from thioxanthone)).

When the alkyl group, alkenyl group, or aryl group represented by R _{22 to} R ₂₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable. R _{22 to} R ₂₄ are preferably alkyl groups from the viewpoint of stability and the like, and particularly preferably unsubstituted alkyl groups.

In general formula (4), Q connecting the acrylic moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ₂₅ —, or —COO—R ₂₅ —, and the alkylene group and the arylene group are represented by R _22. a hydrogen atom from an alkyl group and an aryl group in to R ₂₄ is one group formed by removing. Among these, -CONHR ₂₅ -and -COO-R ₂₅ -are preferable because of polymerizability and availability. R ₂₅ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

  V − in the general formula (4) constituting the counter anion of the resin may be an inorganic or organic anion. As the anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions and iodide ions; carboxylate ions such as formate ions and acetate ions; Complexes such as ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and hexacyanoferrate (III) ions And ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded to the resin to form an inner salt.

  In order to obtain an acrylic resin containing the structural unit represented by the general formula (4), not only a method of copolymerizing a monomer component containing an ethylenically unsaturated monomer having an ammonium base, but also an amino group It may be obtained by a method in which an acrylic resin having an amino group is obtained by copolymerizing a monomer component containing an ethylenically unsaturated monomer, and then reacted with an onium chlorinating agent to be ammonium salified.

  Specific examples of an ethylenically unsaturated monomer having an ammonium base, an ethylenically unsaturated monomer having an amino group, other copolymerizable ethylenically unsaturated monomers, and an onium chloride agent are shown below. Although shown, it is not limited to these, A well-known thing can be used without limit.

(Ethylenically unsaturated monomer having an ammonium base)
Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth) acryloyl. Alkyl (meth) acrylate quaternary ammonium salts such as oxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloylamide quaternary ammonium salts such as dimethyl Allyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

(Ethylenically unsaturated monomer having an amino group)
Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, styrenes having a dialkylamino group such as dimethylaminostyrene, dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

(Other copolymerizable ethylenically unsaturated monomers)
Other copolymerizable ethylenically unsaturated monomers include, for example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( And (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, and the like.

  The acrylic resin containing the structural unit represented by the general formula (4) preferably has a thermally crosslinkable functional group in order to improve the resistance of the coating film. The monomer is preferably a monomer having a crosslinkable functional group. The preferred structure of the thermally crosslinkable functional group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic anhydride, an imino group, an oxetanyl group, a t-butyl group, an epoxy group, a mercapto group, and an isocyanate group (block Isocyanate group), allyl group, (meth) acryl group and the like. Among these, from the viewpoint of storage stability and reactivity with other materials in the use of a coloring composition for a color filter, a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, and a (meth) acryl group are preferable. More preferred are a hydroxyl group, a carboxyl group, an oxetanyl group, and a t-butyl group.

  Two or more types of thermally crosslinkable functional groups may be included. The combined use of an oxetanyl group and a carboxyl group, the combined use of an oxetanyl group and a t-butyl group, the combined use of a hydroxyl group and an isocyanate group, and the combined use of a hydroxyl group and a carboxyl group are particularly preferred.

  The acrylic resin containing the structural unit represented by the general formula (4) preferably has a glass transition temperature (hereinafter abbreviated as Tg) of 50 ° C. or higher. An acrylic resin having a glass transition temperature (hereinafter abbreviated as Tg) of 50 ° C. or higher forms a stronger film in the heating process in the production of a color filter and prevents color change of the film, that is, improves heat resistance. In addition, the solvent resistance is improved.

  As a method for obtaining a resin having a cationic group in the side chain, known methods such as anion polymerization, living anion polymerization, cation polymerization, living cation polymerization, free radical polymerization, and living radical polymerization can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  The amount of the ammonium base present in the resin having a cationic group in the side chain is not particularly limited, but the ammonium salt value of the resin is preferably 10 to 200 mgKOH / g, and 20 to 130 mgKOH / g. It is more preferable that

  The molecular weight of the resin having a cationic group in the side chain is not particularly limited, but the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 500,000. Preferably, it is 3,000-15,000.

  In the resin having a cationic group in the side chain, the total content of the structural unit represented by the general formula (4) is not particularly limited, but the entire structure contained in the resin having a cationic group in the side chain. When the unit is 100% by weight, the total content of the structural unit represented by the general formula (4) is 5% by weight or more from the viewpoint of solvent solubility and coloring power of the salt-forming compound. Preferably, it is 10 to 50% by weight.

(Onium Chloride)
Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chloro bromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

  As an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the resin having a cationic group in the side chain and the xanthene dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

  Moreover, when preparing the salt-forming compound used in the present invention, a resin having a cationic group in the side chain of the same structure relative to the xanthene dye (A1) and the xanthene dye (A2) may be used, or a different structure. A resin having a cationic group in the side chain may be used.

  Further, the xanthene dye (A1) and the xanthene dye (A2) may be mixed and salted simultaneously, or the xanthene dye (A1) and the xanthene dye (A2) may be mixed and then mixed.

  Specific examples of the xanthene dye A1 of the present invention include the following xanthene dyes (XA1) to (XA24) and salt-forming compounds of the dye, but the present invention is not limited thereto.

<Xanthene dye having fluorescence (A2)>
The xanthene dye (A2) having fluorescence is not particularly limited as long as it has fluorescence, but xanthene oil-soluble dyes, xanthene basic dyes, and xanthene acid dyes are preferably used. Among them, in the transmission spectrum, the transmittance is 90% or more in the region of 650 nm, the transmittance is 75% or more in the region of 600 nm, the transmittance is 5% or less in the region of 500 to 550 nm, and the transmittance is 70 in the region of 400 nm. % Or more is preferable. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

[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, CI Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72, CI 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 CI Solvent Violet 10 and 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 basic dye]
Xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.

[Xanthene acid dyes]
The acidic dye of the xanthene dye will be described. As the acid dye of the xanthene dye, 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. Acid Violet 9, C.I. I. Acid violet 30 and those represented by the following general formula (5) are preferably used. Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. It is preferable to use Acid Red 52 or a compound represented by the following general formula (5) (C. I. Acid Red 289, etc.), and among these, a compound represented by General Formula (5) is particularly preferable.

General formula (5)

[In general formula (5),
R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.
Y ₃ and Y ₄ each independently have an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted cycloalkyl group having 5 to 8 carbon atoms, or a substituent. Represents an aryl group having 6 to 10 carbon atoms.
R ₅ and Y ₃ and R ₆ and Y ₄ may be combined to form a ring containing a nitrogen atom. ]

In General Formula (5), it may have a C1-C10 alkyl group which may have a substituent, a C5-C8 cycloalkyl group which may have a substituent, and a substituent. Resin Z ⁺ having an aryl group having 6 to 10 carbon atoms, a ring containing a nitrogen atom, and a cationic group in the side chain is synonymous with the description of the general formulas (1) and (2).

R ₅ and R ₆ are preferably a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 5 carbon atoms. Y ₃ and Y ₄ are preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent or an aryl group having 6 to 10 carbon atoms which may have a substituent. 5 alkyl groups or aryl groups having 6 to 10 carbon atoms which may have a substituent are preferable, and alkyl groups having 1 to 5 carbon atoms substituted with sulfonic acid are particularly preferable.

The xanthene dye (A2) having fluorescence is preferably a xanthene basic dye or a xanthene acid dye, and can also be used as a salt-forming compound or a sulfonic acid amide compound. The xanthene basic dye is preferably used after being salted using 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. The xanthene acid dye is preferably used as a salt-forming compound by salt formation with a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, etc., and a resin component having these functional groups. . As the resin component, the resin Z ⁺ having a cationic group in the side chain is preferably used. Among these, a salt-forming compound of a xanthene acidic dye and a resin Z ⁺ having a cationic group in the side chain is preferable.

  The content of the xanthene dye (A1) is preferably 0.1% by mass to 10.0% by mass, and preferably 0.5% by mass to 5% with respect to the total of the xanthene dye (A1) and the xanthene dye (A2) having fluorescence. 0.0 mass% is more preferable. In addition, when using a xanthene dye as a salt-forming compound, the resin part is not included in the content of the xanthene dye.

<Other colorants>
The colorant of the present invention may contain a dye and / or an organic pigment other than the xanthene dye (A1) represented by the general formula (1) and the xanthene dye (A2) having fluorescence as the other colorant. .

[Organic pigments]
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 as compared with a conventional colorant combining a blue pigment and other pigments.

  Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, JP 2008-19383 Examples thereof include zinc phthalocyanine pigments described in JP-A-2007-320986, JP-A-2004-70342, and the like. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.

  As the green pigment for forming the green filter segment, an aluminum phthalocyanine pigment is also preferably used, and aluminum phthalocyanine pigments described in JP-A Nos. 2004-333817 and 48893859 can also be used.

  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, 1 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, or diketopyrrolopyrrole pigments described in JP-T-2011-523433.

  Examples of orange pigments that work in the same way as red pigments include C.I. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61 can be used. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 254, C.I. I. It is particularly preferable to use Pigment Red 177.

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

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

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

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

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

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

[dye]
The coloring composition for a color filter of the present invention is not particularly limited as long as it is a dye other than the xanthene dye (A1) represented by the general formula (1) and the xanthene dye (A2) having fluorescence, and a known dye is used. can do. For example, xanthene dyes other than the xanthene dye (A1) represented by the general formula (1) and the fluorescent xanthene dye (A2), azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, Examples include quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes.

<Resin>
The resin is one that disperses a colorant, particularly the xanthene dye of the present invention, a salt-forming compound thereof, and a pigment, or those that dye or infiltrate them, and examples thereof include thermoplastic resins and thermosetting resins. The spectral transmittance in the entire wavelength region of 400 to 700 nm in the visible light region of the resin is preferably 80% or more, more preferably 95% or more.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

  Further, when the colored composition for a color filter of the present invention is used in the form of an alkali development type colored resist material, an alkali-soluble resin is preferably used, and an alkali-soluble copolymer obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. It is preferable to use a vinyl resin.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and 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.

  In order to improve the photosensitivity of the alkali-soluble resin copolymerized with the acidic group-containing ethylenic non-monomer, an energy beam curable resin having an ethylenically unsaturated active double bond can also be used. In addition, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain because it has an effect of improving the solvent resistance of the resist material.

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

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

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

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

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

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

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

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

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

  The weight average molecular weight (Mw) of the 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.

  The resin is compatible with the colorant adsorbing group and the carboxyl group acting as an alkali-soluble group during development, a colorant carrier, and a solvent from the viewpoints of dispersibility, permeability, developability, and heat resistance of the pigment and salt-forming compound. The balance between the aliphatic group and aromatic group acting as a group is important for the dispersibility, penetrability, developability, and durability of the pigment and salt-forming compound, and a resin having an acid value of 20 to 300 mgKOH / g should be used. Is preferred. 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 resin is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight) from the viewpoint of film formability and various resistances, and has a high colorant concentration and can exhibit good color characteristics. Therefore, it is preferably used in an amount of 500% by weight or less.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation.

  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, because of good dispersion and dissolution of the colorant of the present invention, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate It is preferable to use alcohols such as 3-methoxybutanol and benzyl alcohol and ketones such as cyclohexanone. In particular, ethyl lactate, propylene glycol monomethyl ether acetate, and 3-methoxybutanol are more preferable from the viewpoint of safety and health and low viscosity.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When two or more kinds of mixed solvents are used, it is preferable that 65 to 95% by weight of the above-mentioned preferable organic solvent is contained.

  In addition, since the organic solvent can adjust the colored composition to an appropriate viscosity to form a filter segment having a desired uniform film thickness, it is 800 to 4000 weights based on the total weight of the colorant (100 weight%). % Is preferably used.

<Dispersion>
When the coloring composition of the present invention contains a pigment, it is preferably finely dispersed by 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. It can be dispersed and manufactured. The colored composition of the present invention can also be produced by mixing xanthene dyes, other colorants and the like separately dispersed in a colorant carrier.

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

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group 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. It can use individually or in mixture of 2 or more types.

  The blending amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, most preferably from the viewpoint of improving the dispersibility of the additive pigment, based on the total amount of the additive pigment (100% by weight). 3% by weight or more. Further, from the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount (100% by weight).

(Resin type dispersant)
The resin-type dispersant has a pigment-affinity part that has the property of adsorbing to the additive pigment and a part that is compatible with the colorant carrier, and adsorbs to the additive pigment 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, used phosphoric acid ester and the like, they may be used alone or in combination, 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, 16000, 17 manufactured by Nippon Lubrizol Co., Ltd., such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen 00, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Japan Manufactured by EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Moreover, as a polyester-type dispersing agent, the dispersing agent manufactured by the well-known method of WO2008 / 007776, Unexamined-Japanese-Patent No. 2009-155406, and Unexamined-Japanese-Patent No. 2010-185934 can be used.

(Surfactant)
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 may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The amount of the resin-type dispersant and surfactant added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the added pigment (100% by weight). It is. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. May affect.

<Photopolymerizable monomer>
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more. The blending amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, ru (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator>
The colored composition for a color filter of the present invention is a solvent development type or alkali development type colored resist material added with a photopolymerization initiator or the like when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method. It can be prepared in the form of The blending amount when using the photopolymerization initiator is preferably 5 to 200% by weight based on the total amount of the colorant, and 10 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -S-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( 4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1- (N-4-benzoylphenyl-carbazol-3-yl) -butane-1,2-dione-2-oxy -O-acetate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl]-, 1- (0-acetyloxime), or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, etc. Oxime ester compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone Quinone compounds such as ethyl anthraquinone; borate compounds; carbazole compounds; Zole compounds; or titanocene compounds are used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant in the color filter coloring composition (100% by weight), and 10 from the viewpoint of photocurability and developability. More preferably, it is -150 weight%.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, 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 derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone 4,4′-diethylaminobenzophenone and the like.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

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

<Amine compound>
Moreover, the coloring composition 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 colored composition 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. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

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

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

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

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Removal of coarse particles>
The colored composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove 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 this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment, or those having a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are 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, etc. in addition to the above method, but the colored 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.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”. PGMAc represents propylene glycol monomethyl ether acetate.

<Identification of xanthene dye>
The xanthene dye was identified by mass spectrometry.
<< Mass Spectrometry >> LC: Agilent 1200 model, MASS: Agilent LC / MSD model was used for analysis.

<Production of resin solution>
(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 further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26,000. 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. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. This was added to prepare an alkali-soluble resin solution 1. Here, the weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. About 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight, and an alkali-soluble resin solution. 2 was prepared. The weight average molecular weight (Mw) was 18,000.

(Resin solution 3)
After introducing 123 g of cyclohexanone into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device, the atmosphere in the flask is changed from air to nitrogen, and then the temperature is raised to 100 ° C. 72.6 g (0.41 mol), methacrylic acid 42.0 g (0.49 mol), tricyclodecane skeleton monomethacrylate (Hitachi Chemical Co., Ltd. FA-513M) 23.0 g (0.10 mol) and A solution obtained by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 137 g of cyclohexanone was dropped into the flask over 2 hours from the dropping funnel, and the stirring was further continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 21.3 g of glycidyl methacrylate [0.15 mol, (31 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours. About 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight, and an alkali-soluble resin solution. 3 was prepared. The weight average molecular weight (Mw) was 10,500.

(Resin solution 4)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and the reaction was terminated when the solid content acid value reached 0.5 to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an alkali-soluble resin solution 4 was prepared. The weight average molecular weight (Mw) was 19,000.

<Preparation of resin-type dispersant solution>
(Resin Dispersant Solution 1)
A resin type dispersant solution 1 having a nonvolatile content of 40% by weight was prepared using EFKA4300 manufactured by BASF, which is a commercially available resin type dispersant, and ethylene glycol monomethyl ether acetate.

(Resin Dispersant Solution 2)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, 41.8 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, t-butyl 16.0 parts of acrylate, 10.0 parts of hydroxymethyl methacrylate and 2.0 parts of ethyl acrylate were added, and 0.10 parts of AIBN and 60.0 parts of PGMAc were added and reacted for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. PGMAc was added to adjust the non-volatile content to 40% to obtain a resin type dispersant solution 2 having an acid value of 43 and a weight average molecular weight of 15000.

<Production of resin Z ⁺ having a cationic group in the side chain>
(Resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6,830, and then cooled to 50 ° C. To this solution, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a resin 1 solution having a cationic group in the side chain of 47% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

  Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value of the resin having a cationic group in the side chain was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent amount of potassium hydroxide. It indicates the ammonium salt value of the solid content.

(Resin 2 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 2,2′-azobis (2,4-dimethylvaleronitrile 5.7) and 15.6 parts of methyl ethyl ketone were made uniform, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7,420, and then cooled to 50 ° C. 72 parts of isopropyl alcohol was added to this solution to obtain a resin 2 solution having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Resin 3 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 82.0 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 23.5 parts of ethyl methacrylate, 26.0 parts of t-butyl methacrylate, 25.0 parts of lauryl methacrylate, Kayamer PM-21 (manufactured by Nippon Kayaku Co., Ltd., 1 mol of ε-caprolaclone 1-hydroxyethyl methacrylate phosphate ester) ) 10.0 parts, diethylaminopropyl methacrylate 17.5 parts, 2,2′-azobis (2,4-dimethylvaleronitrile) 6.0 parts, and methyl ethyl ketone 25.6 parts, and then a dropping funnel Was attached to a four-necked separable flask and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7,010, and then cooled to 50 ° C. In this manner, a resin 3 solution having a cationic group in the side chain of 48% by weight of the resin component was obtained. The amine value of the obtained resin was 49 mgKOH / g. Here, the amine value of the resin having a cationic group in the side chain was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent amount of potassium hydroxide.

(Resin 4 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 2.5 parts of methacrylic acid, 15.0 parts of hydroxyethyl methacrylate, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 7.6 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride , 2,2'-azobis (2,4-dimethylvaleronitrile) 5.7 parts and methyl ethyl ketone 15.6 parts were made uniform and charged into a dropping funnel and attached to a four-necked separable flask for 2 hours. It was dripped over. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7,420, and then cooled to 50 ° C. 72 parts of isopropyl alcohol was added to this solution to obtain a resin 4 solution having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Resin 5 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 2.5 parts of methacrylic acid, 15.0 parts of 3- (acryloyloxymethyl) 3-methyloxetane, 32.1 parts of t-butyl methacrylate, 25.1 parts of n-propyl methacrylate, 7.6 parts of lauryl methacrylate, After uniformizing 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 5.7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile), and 15.6 parts of methyl ethyl ketone, the mixture was charged into a dropping funnel. It was attached to a one-necked separable flask and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7,420, and then cooled to 50 ° C. 72 parts of isopropyl alcohol was added to this solution to obtain a resin 5 solution having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Resin 6 having a cationic group in the side chain)
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 2.5 parts of methacrylic acid, 15.0 parts of 3- (acryloyloxymethyl) 3-methyloxetane, t-butyl methacrylate 32. 1 part, 25.1 parts of n-propyl methacrylate and 7.6 parts of lauryl methacrylate were charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was raised to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion was 98% or more in terms of non-volatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 17.7 parts of methacryloylaminopropyltrimethylammonium chloride as the second block monomer were added to this reactor, and the reaction was stirred while maintaining a nitrogen atmosphere at 100 ° C. Continued. After 2 hours from the introduction of dimethylaminoethyl methyl chloride salt, the polymerization solution is sampled to measure the solid content, and converted from the nonvolatile content to confirm that the polymerization conversion rate of the second block is 98% or more. The solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the polymer had Mw of 9,200 and Mw / Mn = 1.5, and the reaction conversion rate was 98.5%. In this way, Resin 6 having a cationic group in the block side chain having a quaternary ammonium salt value of 45 mg KOH / g per solid content was obtained. 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, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight. A solution of Resin 6 having a cationic group in the side chain was obtained.

<Production 1 of xanthene dye (A1)>
[Example 1-1]
(Xanthene dye (XA1))
20 mmol of the compound represented by the formula (6) and 80 mmol of 5-amino-2-benzimidazolinone were added to 50 g of N-methylpyrrolidone and stirred at 100 ° C. for 10 hours. After cooling to room temperature, the reaction solution was added to 750 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA1).

Formula (6)

[Example 1-2]
(Xanthene dye (XA2))
16 mmol of xanthene dye (XA1) was added to 80 g of N-methylpyrrolidone, 56 mmol of tripotassium phosphate and 56 mmol of 1-iodobutane were added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA2).

[Example 1-3]
(Xanthene dye (XA3))
20 mmol of the compound represented by the formula (6) and 20 mmol of 2,6-dimethylaniline were added to 50 g of N-methylpyrrolidone and stirred at 80 to 90 ° C. for 2 hours. Two hours later, 60 mmol of 5-amino-2-benzimidazolinone was added, and the mixture was further stirred at 100 ° C. for 4 hours. After cooling to room temperature, the reaction solution was added to 750 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA3).

[Example 1-4]
(Xanthene dye (XA4))
16 mmol of xanthene dye (XA3) was added to 80 g of N-methylpyrrolidone, 56 mmol of tripotassium phosphate and 56 mmol of 1-iodopropane were added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA4).

[Example 1-5]
(Xanthene dye (XA5))
16 mmol of xanthene dye (XA3) was added to 80 g of N-methylpyrrolidone, 80 mmol of tripotassium phosphate and 80 mmol of 2-iodopropane were added, and the mixture was stirred at 80 ° C. for 8 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA5).

[Example 1-6]
(Xanthene dye (XA6))
In the synthesis of xanthene dye (XA4), xanthene dye (XA6) was obtained in the same manner as in Example 1-4 except that 2-bromoethyl methyl ether was added instead of 1-iodopropane.

[Example 1-7]
(Xanthene dye (XA7))
20 mmol of the compound represented by the formula (6) and 20 mmol of 2,6-dimethylaniline were added to 50 g of N-methylpyrrolidone and stirred at 80 to 90 ° C. for 2 hours. After 2 hours, 60 mmol of 5-amino-6-methyl-2-benzimidazolinone was added, and the mixture was further stirred at 100 ° C. for 4 hours. After cooling to room temperature, the reaction solution was added to 750 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain a xanthene dye intermediate. 16 mmol of the obtained xanthene dye intermediate was added to 80 g of N-methylpyrrolidone, 56 mmol of tripotassium phosphate and 56 mmol of 1-iodopropane were added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA7).

[Example 1-8]
(Xanthene dye (XA8))
In the synthesis of xanthene dye (XA7), the same as Example 1-7, except that 5-amino-6-methoxy-2-benzimidazolinone was added instead of 5-amino-6-methyl-2-benzimidazolinone And xanthene dye (XA8) was obtained.

[Example 1-9]
(Xanthene dye (XA9))
16 mmol of xanthene dye (XA3) obtained in Example 1-3 was added to 80 g of N-methylpyrrolidone, 80 mmol of tripotassium phosphate and 80 mmol of 1-iodopropane were added, and the mixture was stirred at 90 ° C. for 6 hours. . After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA9).

[Example 1-10]
(Xanthene dye (XA10))
20 mmol of the compound represented by the formula (6) and 20 mmol of 2,6-dimethoxyaniline were added to 50 g of N-methylpyrrolidone and stirred at 80 to 90 ° C. for 2 hours. Two hours later, 60 mmol of 5-amino-2-benzimidazolinone was added, and the mixture was further stirred at 100 ° C. for 4 hours. After cooling to room temperature, the reaction solution was added to 750 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain a xanthene dye intermediate. 16 mmol of the obtained xanthene dye intermediate was added to 80 g of N-methylpyrrolidone, 56 mmol of tripotassium phosphate and 56 mmol of 1-iodopropane were added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA10).

[Example 1-11]
(Xanthene dye (XA11))
In the synthesis of xanthene dye (XA4), xanthene dye (XA11) was synthesized in the same manner as in Example 1-4 except that 4-bromo-2,6-dimethylaniline was added instead of 2,6-dimethylaniline. )

[Example 1-12]
(Xanthene dye (XA12))
20 mmol of the compound represented by the formula (6) and 20 mmol of 5-amino-2-benzimidazolinone were added to 50 g of N-methylpyrrolidone and stirred at room temperature for 2 hours. After 2 hours, 60 mmol of morpholine was added, and the mixture was further stirred at 100 ° C. for 4 hours. After cooling to room temperature, the reaction solution was added to 750 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain a xanthene dye intermediate. 16 mmol of the obtained xanthene dye intermediate was added to 80 g of N-methylpyrrolidone, 56 mmol of tripotassium phosphate and 56 mmol of 1-iodopropane were added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA12).

[Example 1-13]
(Xanthene dye (XA13))
In the synthesis of xanthene dye (XA12), synthesis was performed in the same manner as in Example 1-12 except that trans-decahydroquinoline was added instead of morpholine, to obtain xanthene dye (XA13).

[Example 1-14]
(Xanthene dye (XA14))
In the synthesis of xanthene dye (XA12), synthesis was performed in the same manner as in Example 1-12 except that diethanolamine was added instead of morpholine to obtain xanthene dye (XA14).

[Example 1-15]
(Xanthene dye (XA15))
In the synthesis of xanthene dye (XA12), synthesis was performed in the same manner as in Example 1-12 except that dibenzylamine was added instead of morpholine to obtain xanthene dye (XA15).

[Example 1-16]
(Xanthene dye (XA16))
In the synthesis of xanthene dye (XA12), synthesis was performed in the same manner as in Example 1-12 except that N-ethylcyclohexylamine was added instead of morpholine to obtain xanthene dye (XA16).

[Example 1-17]
(Xanthene dye (XA17))
20 mmol of the compound represented by the formula (6) and 20 mmol of 5-amino-2-benzimidazolinone were added to 50 g of N-methylpyrrolidone and stirred at room temperature for 2 hours. After 2 hours, 60 mmol of dibutylamine was added, and the mixture was further stirred at 100 ° C. for 4 hours. After cooling to room temperature, the reaction solution was added to 750 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA17).

[Example 1-18]
(Xanthene dye (XA18))
16 mmol of xanthene dye (XA17) was added to 80 g of N-methylpyrrolidone, 56 mmol of tripotassium phosphate and 56 mmol of 1-iodopropane were added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA18).

[Example 1-19]
(Xanthene dye (XA19))
In the synthesis of xanthene dye (XA18), xanthene dye (XA19) was obtained in the same manner as in Example 1-18 except that sodium 3-bromopropanesulfonate was added instead of 1-iodopropane.

[Example 1-20]
(Xanthene dye (XA20))
16 mmol of xanthene dye (XA17) was added to 80 g of N-methylpyrrolidone, 80 mmol of tripotassium phosphate and 80 mmol of 1-iodobutane were added, and the mixture was stirred at 90 ° C. for 6 hours. After cooling to room temperature, the reaction solution was added to 800 g of water to precipitate the dye. The obtained solid was filtered off, washed with 750 g of water, and dried to obtain xanthene dye (XA20).

[Example 1-21]
(Xanthene dye (XA21))
The xanthene dye (XA3) was synthesized in the same manner as in Example 1-3 except that sodium 4-amino-3-methylbenzenesulfonate tetrahydrate was added instead of 2,6-dimethylaniline. A xanthene dye (XA21) was obtained.

[Example 1-22]
(Xanthene dye (XA22))
To the sulfuric acid obtained by mixing 11.6 g of 98% sulfuric acid and 3.4 g of fuming sulfuric acid (SO ₃ content 30%), 1.0 g of the xanthene dye (XA3) obtained in Example 1-3 was slightly added over 1 hour. The solution was added in portions and stirred at room temperature for 2 hours. The reaction solution was added to 150 g of water to precipitate the pigment. The obtained solid was filtered off and dried to obtain a xanthene dye (XA22).

[Example 1-23]
(Xanthene dye (XA23))
In the synthesis of xanthene dye (XA22), xanthene dye (XA23) was obtained in the same manner as in Example 1-22, except that (XA4) was added instead of xanthene dye (XA3).

[Example 1-24]
(Xanthene dye (XA24))
In the synthesis of xanthene dye (XA22), xanthene dye (XA24) was obtained in the same manner as in Example 1-22, except that (XA9) was added instead of xanthene dye (XA3).

<Production 2 of xanthene dye (A1) (salt-forming compound)>
[Example 1-23-1]
(Xanthene dye-forming salt (XA23-c1))
A solution of resin 1 having a cationic group in the side chain of 62.0 parts was added to 1500 parts of water, and after sufficiently stirring and mixing, the resin solution was prepared by heating to 60 ° C. On the other hand, an aqueous solution in which 10.0 parts of xanthene dye (XA23) was dissolved in 100 parts of a 10% aqueous methanol solution was prepared and added dropwise little by little to the previously prepared resin solution. After completion of the dropwise addition, the reaction was performed by stirring at 30 ° C. for 90 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 35.3 parts of salt-forming compound (XA23- c1) was obtained. The content of the effective dye component derived from the xanthene dye (XA23) in the obtained salt-forming compound (XA23-c1) was 25% by mass.

[Example 1-23-2]
(Xanthene dye-forming salt (XA23-c2))
A resin solution having a cationic group in the side chain of 44 parts was added to 1500 parts of a 10% aqueous methanol solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. to prepare a resin solution. On the other hand, an aqueous solution in which 10.0 parts of xanthene dye (XA23) was dissolved in 100 parts of a 10% aqueous methanol solution was prepared and added dropwise little by little to the previously prepared resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 21.6 parts of salt-forming compound (XA23 -C2) was obtained. At this time, the content of the effective pigment component derived from the xanthene pigment (XA23) in the salt-forming compound (XA23-c2) was 24% by mass.

[Example 1-23-3]
(Xanthene dye-forming salt (XA23-c3))
After adding a solution of resin 3 having a cationic group in the side chain of 63.2 parts to 2000 parts of 20% acetic acid and sufficiently stirring and mixing, the mixture was heated to 60 ° C. and the tertiary amino group of the side chain was Ammonium chloride was performed. On the other hand, an aqueous solution in which 10.0 parts of xanthene dye (XA23) was dissolved in 90 parts of water was prepared, and the resulting solution was dropped little by little into the ammonium chloride resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 39 parts of the salt-forming compound (XA23-c3 ) At this time, the content of the effective dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c3) was 25% by mass.

[Example 1-23-4]
(Xanthene dye-forming salt (XA23-c4))
A resin solution having a cationic group in a side chain of 42 parts was added to 1500 parts of a 10% aqueous methanol solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. to prepare a resin solution. On the other hand, an aqueous solution in which 10.0 parts of xanthene dye (XA23) was dissolved in 100 parts of a 10% aqueous methanol solution was prepared and added dropwise little by little to the previously prepared resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 23 parts of the salt-forming compound (XA23-c4 ) At this time, the content of the effective dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c4) was 25% by mass.

[Example 1-2-3-5]
(Xanthene dye-forming salt (XA23-c5))
A solution of resin 5 having a cationic group in the side chain of 43 parts was added to 1500 parts of a 10% aqueous methanol solution, sufficiently mixed with stirring, and then heated to 60 ° C. to prepare a resin solution. On the other hand, an aqueous solution in which 10.0 parts of xanthene dye (XA23) was dissolved in 100 parts of a 10% aqueous methanol solution was prepared and added dropwise little by little to the previously prepared resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 25 parts of the salt-forming compound (XA23-c5 ) At this time, the content of the effective pigment component derived from the xanthene pigment (XA23) in the salt-forming compound (XA23-c5) was 26% by mass.

[Example 1-2-3]
(Xanthene dye-forming salt (XA23-c6))
A solution of resin 6 having a cationic group in the side chain of 43 parts was added to 1500 parts of a 10% aqueous methanol solution, sufficiently mixed with stirring, and then heated to 60 ° C. to prepare a resin solution. On the other hand, an aqueous solution in which 10.0 parts of xanthene dye (XA23) was dissolved in 100 parts of a 10% aqueous methanol solution was prepared and added dropwise little by little to the previously prepared resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 26 parts of the salt-forming compound (XA23-c6 ) At this time, the content of the effective dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c6) was 25% by mass.

[Example 1-2-1-6]
(Xanthene dye-forming salt (XA21-c6))
In the synthesis of xanthene dye (XA23-c6), synthesis was performed in the same manner as in Example 1-26 except that (XA21) was added instead of (XA23), and the xanthene dye salt-forming compound (XA21-c6) was synthesized. ) At this time, the content of the effective dye component derived from the xanthene dye (XA21) in the salt-forming compound (XA21-c6) was 25% by mass.

[Example 1-2-22-6]
(Xanthene dye-forming salt (XA22-c6))
The xanthene dye (XA23-c6) was synthesized in the same manner as in Example 1-26 except that (XA22) was added instead of (XA23), and the xanthene dye salt-forming compound (XA22-c6) was synthesized. ) At this time, the content of the effective dye component derived from the xanthene dye (XA12) in the salt-forming compound (XA22-c6) was 25% by mass.

[Example 1-24-6]
(Xanthene dye-forming salt (XA24-c6))
In the synthesis of xanthene dye (XA23-c6), xanthene dye (XA24-c6) was synthesized in the same manner as in Example 23-23-6 except that xanthene dye (XA24) was added instead of xanthene dye (XA23). )

  The structures of the obtained xanthene dyes (X1) to (X24) are shown below. The substituent structure is summarized in Table 1. [Example 1-1] (XA1) and [Example 1-2] (XA2) are reference examples.

<Production of fluorescent xanthene dye (A2)>
(Fluorescent xanthene dye (XA33))
C. I. 16 mmol of Acid Red 289 was added to 80 g of N-methylpyrrolidone, 56 mmol of tripotassium phosphate and 56 mmol of 1-iodopropane were added, and the mixture was stirred at 90 ° C. for 3 hours. After cooling to room temperature, excess tripotassium phosphate was removed by filtration, added to 800 parts of ethyl acetate, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected by filtration, washed with 800 parts of ethyl acetate, and then dried to obtain xanthene dye (XA33).

Xanthene dye (XA33)

(Fluorescent xanthene dye-forming salt (XA33-c1))
In the synthesis of xanthene dye (XA23-c1), xanthene dye (XA33-c1) was synthesized in the same manner as in Example 1-23-1 except that xanthene dye (XA33) was added instead of xanthene dye (XA23). ) At this time, the content of the effective dye component derived from the xanthene dye (XA33) in the salt-forming compound (XA33-c1) was 25% by mass.

(Fluorescent xanthene dye-forming salt (XA33-c2))
In the synthesis of xanthene dye (XA23-c2), xanthene dye (XA33-c2) was synthesized in the same manner as in Example 1-2-3 except that xanthene dye (XA33) was added instead of xanthene dye (XA23). ) At this time, the content of the effective dye component derived from the xanthene dye (XA33) in the salt-forming compound (XA33-c2) was 25% by mass.

(Fluorescent xanthene dye-forming salt (XA33-c3))
In the synthesis of xanthene dye (XA23-c3), xanthene dye (XA33-c3) was synthesized in the same manner as in Example 1-23-3 except that xanthene dye (XA33) was added instead of xanthene dye (XA23). ) At this time, the content of the effective dye component derived from the xanthene dye (XA33) in the salt-forming compound (XA33-c3) was 25% by mass.

(Fluorescent xanthene dye-forming salt (XA33-c4))
In the synthesis of xanthene dye (XA23-c4), xanthene dye (XA33-c4) was synthesized in the same manner as in Example 1-23-4 except that xanthene dye (XA33) was added instead of xanthene dye (XA23). ) At this time, the content of the effective dye component derived from the xanthene dye (XA33) in the salt-forming compound (XA33-c4) was 25% by mass.

(Fluorescent xanthene dye-forming salt (XA33-c5))
In the synthesis of xanthene dye (XA23-c5), xanthene dye (XA33-c5) was synthesized in the same manner as in Example 1-23-5 except that xanthene dye (XA33) was added instead of xanthene dye (XA23). ) At this time, the content of the effective dye component derived from the xanthene dye (XA33) in the salt-forming compound (XA33-c5) was 25% by mass.

(Fluorescent xanthene dye-forming salt (XA33-c6))
In the synthesis of xanthene dye (XA23-c6), xanthene dye (XA33-c6) was synthesized in the same manner as Example 1-23-6 except that xanthene dye (XA33) was added instead of xanthene dye (XA23). ) At this time, the content of the effective dye component derived from the xanthene dye (XA33) in the salt-forming compound (XA33-c6) was 25% by mass.

(Fluorescent xanthene dye-forming salt (XA23,33-c6))
A solution of resin 6 having a cationic group in the side chain of 43 parts was added to 1500 parts of a 10% aqueous methanol solution, sufficiently mixed with stirring, and then heated to 60 ° C. to prepare a resin solution. On the other hand, an aqueous solution in which 0.3 part of xanthene dye (XA23) and 9.7 parts of xanthene dye (XA33) was dissolved in 100 parts of a 10% aqueous methanol solution was prepared and added dropwise to the previously prepared resin solution. did. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 28 parts of the salt-forming compound (XA23,33) -C6) was obtained. At this time, the content of the effective pigment component derived from the xanthene pigments (XA23) and (XA33) in the salt-forming compound (XA23,33-c6) was 25% by mass.

<Adjustment of coloring composition for color filter>
[Example 2-1]
(Coloring composition DA-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. Xanthene dye (XA1): 0.09 parts Fluorescent xanthene dye (XA33-c6): 11.64 parts Resin solution 1: 13.35 parts Propylene glycol monomethyl Ether acetate: 74.92 parts

[Examples 2-2 to 52 and Comparative Examples 2-1 to 6]
(Coloring composition DA-2 to 58)
Hereinafter, as shown in Table 2, colored compositions (DA-2 to 58) were obtained in the same manner as the colored composition (DA-1) except that the composition and the blending amount were changed.

<Evaluation of coloring composition for color filter>
The contrast ratio of the obtained colored composition (DA-1 to 58) was evaluated by the following method. The results are shown in Table 2.

(Contrast ratio)
The coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the film thickness of the dried coating film was 1.2 μm, and the oven was heated at 230 ° C. for 20 minutes. Firing was performed to produce a coated substrate. The contrast ratio (CR) was measured using the obtained coated substrate. 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, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. Judgment criteria are as follows. In the evaluation results, ◯ is a good result, Δ is a level that causes some problems but there is no problem in use, and × corresponds to inappropriate use.
○: 10000 or more Δ: 7000 or more, less than 10000 ×: less than 7000

Abbreviations shown in Table 2 are shown below.
(Xanthene dye (XA31, XA32))

(Phthalocyanine dye (compound B))

(Cyanine dye having fluorescence (Compound C))
A resin having an anionic group in the same manner as the fluorescent dye (A-11) in JP-A-2015-18208; I. A cyanine dye (compound C) having fluorescence, which is a salt-forming compound with Basic Red 12, was obtained.

  The colored composition of the present invention containing the xanthene dye (A1) having a benzimidazolone group and the fluorescent xanthene dye (A2) represented by the general formula (1) has an excellent contrast ratio. It is considered that the fluorescence of the xanthene dye (A2) is suppressed by the benzimidazolone group of the dye (A2).

<Production of colorant-containing composition>
(Blue composition (P-1): PB15: 6)
C. I. Pigment Blue 15: 6 (PB15: 6) (11.0 parts of “LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., 35.0 parts of resin solution 1, 5 parts of resin type dispersant solution, propylene glycol monomethyl ether acetate After stirring and mixing 49 parts uniformly, using a zirconia bead with a diameter of 0.5 mm, the mixture was dispersed for 3 hours with an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan), filtered through a 5 μm filter, A blue composition (P-1) was produced.

[Example 2-53]
(Blue composition (P-2): Xanthene dye / PB15: 6)
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 blue composition (P-2) was produced by filtering with a filter.
Xanthene dye (XA23-c6): 0.02 parts Fluorescent xanthene dye (XA33-c6): 2.33 parts PB15: 6 pigment: 8.80 parts Resin-type dispersant solution 1: 4.00 parts Resin solution 1:30 .68 parts propylene glycol monomethyl ether acetate: 54.17 parts

[Example 2-54]
(Blue composition (P-3): Xanthene dye / PB15: 6)
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 blue composition (P-3) was produced by filtering with a filter.
Fluorescent xanthene dye (XA23,33-c6): 2.35 parts PB15: 6 pigment: 8.80 parts Resin-type dispersant solution 1: 4.00 parts Resin solution 1: 30.68 parts Propylene glycol monomethyl ether acetate: 54 .17 parts

[Example 2-55]
(Blue composition (P-4): Xanthene dye / PB15: 6)
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 blue composition (P-4) was produced by filtering with a filter.
Fluorescent xanthene dye (XA23,33-c6): 2.35 parts PB15: 6 pigment: 8.80 parts Resin-type dispersant solution 2: 4.00 parts Resin solution 1: 30.68 parts Propylene glycol monomethyl ether acetate: 54 .17 parts

(Red composition (P-5): PR254)
C. I. Pigment Blue 15: 6 to C.I. I. Pigment Red 254 (PR254) ("IRGAPHOR RED B-CF" manufactured by BASF) was used, except that the red composition (P-5) of PR254 was prepared in the same manner as the blue composition (P-1). Produced.

(Red composition (P-6): PR177)
C. I. Pigment Blue 15: 6 to C.I. I. A PR177 red composition (P-6) was prepared in the same manner as the blue composition (P-1) except that it was changed to CI Pigment Red 177 (PR177) ("A2B" manufactured by BASF).

(Green composition (P-7): PG58)
C. I. Pigment Blue 15: 6 to C.I. I. A green composition (P-7) of PG58 was produced by the same production method as that of the blue composition (P-1) except that the pigment was changed to CI Pigment Green 58 (PG58) (“A110” manufactured by DIC Corporation).

(Yellow composition (P-8): PY150)
C. I. Pigment Blue 15: 6 to C.I. I. A yellow composition (P-8) of PY150 was produced by the same production method as that of the blue composition (P-1) except that it was changed to CI Pigment Yellow 150 (PY150) ("E4GN" manufactured by LANXESS).

<Production of photosensitive coloring composition for color filter>
[Example 3-1]
(Photosensitive coloring composition (RB-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (RB-1).
PB15: 6 blue composition (P-1): 40.0 parts Colored composition for color filter (DA-1): 10.0 parts Resin solution 1: 7.5 parts Photopolymerizable monomer: 2.0 Part (dipentaerythritol hexaacrylate)
Photopolymerization initiator: 1.0 part (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF))
Photopolymerization initiator: 0.5 part (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ( “Irgacure OXE02” manufactured by BASF)
Organic solvent: 39.0 parts (propylene glycol monomethyl ether acetate)

[Examples 3-2 to 52, Comparative examples 3-1 to 6]
(Photosensitive coloring composition (RB-2 to 52, 56 to 61))
The photosensitive colored composition (RB-2 to 52-52) was the same as the photosensitive colored composition (RB-1) except that the types of the colored composition, the blue composition, and the resin solution were changed as shown in Table 3. 55-60). Here, the blending amounts (parts by mass) of the blue composition and the coloring composition are such that when the coated substrate is prepared, after firing at 230 ° C., x = 0.150 and y = 0.060 with a C light source. The ratio was selected to match the chromaticity. The total of the blue composition and the colored composition is 50.0 parts.

[Example 3-53]
(Photosensitive coloring composition (RB-53))
After stirring and mixing so as to be uniform at the following ratio, the mixture was filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-53).
Blue composition (P-2): Xanthene dye / PB15: 6: 50.0 parts Resin solution 1: 7.5 parts Photopolymerizable monomer: 2.0 parts (dipentaerythritol hexaacrylate)
Photopolymerization initiator: 1.0 part (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF))
Photopolymerization initiator: 0.5 part (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ( “Irgacure OXE02” manufactured by BASF)
Organic solvent: 39.0 parts (propylene glycol monomethyl ether acetate)

[Example 3-54]
(Photosensitive coloring composition (RB-54))
After stirring and mixing so as to be uniform at the following ratio, the mixture was filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-54).
Blue composition (P-3): Xanthene dye / PB15: 6: 50.0 parts Resin solution 1: 7.5 parts Photopolymerizable monomer: 2.0 parts (dipentaerythritol hexaacrylate)
Photopolymerization initiator: 1.0 part (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF))
Photopolymerization initiator: 0.5 part (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ( “Irgacure OXE02” manufactured by BASF)
Organic solvent: 39.0 parts (propylene glycol monomethyl ether acetate)

[Example 3-55]
(Photosensitive coloring composition (RB-55))
After stirring and mixing so as to be uniform at the following ratio, the mixture was filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-55).
Blue composition (P-4): Xanthene dye / PB15: 6: 50.0 parts Resin solution 1: 7.5 parts Photopolymerizable monomer: 2.0 parts (dipentaerythritol hexaacrylate)
Photopolymerization initiator: 1.5 parts (1- (N-4-benzoylphenyl-carbazol-3-yl) -butane-1,2-dione-2-oxime-O-acetate)
Organic solvent: 39.0 parts (propylene glycol monomethyl ether acetate)

<Evaluation of photosensitive coloring composition for color filter>
About the obtained photosensitive coloring composition, evaluation of the brightness (spectral transmittance) and contrast ratio (CR) was performed by the following method. The results are shown in Table 3.

(Brightness (spectral transmittance))
The photosensitive coloring composition was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm with a spin coater, exposed to ultraviolet rays at an exposure amount of 50 mJ / cm ² , and then 0.2 mass% carbonic acid at 23 ° C. Spray development was carried out with an aqueous sodium solution for 30 seconds, followed by baking at 230 ° C. for 30 minutes in an oven to obtain a coated substrate of the obtained photosensitive coloring composition. The brightness (spectral transmittance) was measured using the obtained coated substrate. In addition, the blue coating film by a photosensitive coloring composition was apply | coated so that it might match | combine chromaticity of x = 0.150 and y = 0.060 in C light source after baking at 230 degreeC. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. In the evaluation results, “◯” indicates a satisfactory result, and “Δ” corresponds to a level at which there is no problem in use although there are some problems.
○: 11.8 or more △: 11.5 or more, less than 11.8 ×: less than 11.5

(Contrast ratio)
The contrast ratio (CR) was measured using the same substrate as the coated substrate used for brightness measurement. Judgment criteria are as follows. In the evaluation results, “◯” indicates a satisfactory result, and “Δ” corresponds to a level at which there is no problem in use although there are some problems.
○: 11,000 or more Δ: 8000 or more, less than 11000 ×: less than 8000

  The photosensitive coloring composition of the present application containing the xanthene dye (A1) and the fluorescent xanthene dye (A2) is excellent not only in lightness but also in the contrast ratio. This is the effect of suppressing the fluorescence of the xanthene dye (A2). It is thought that.

<Manufacture of color filters>
(Production of red photosensitive coloring composition (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).
PR254 red composition (P-5): 30.0 parts PR177 red composition (P-6): 20.0 parts Resin solution 1: 7.5 parts Photopolymerizable monomer: 2.0 parts (dipenta Erythritol hexaacrylate)
Photopolymerization initiator: 1.0 part (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF))
Photopolymerization initiator: 0.5 part (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ( “Irgacure OXE02” manufactured by BASF)
Organic solvent: 39.0 parts (ethylene glycol monomethyl ether acetate)

(Production of green photosensitive coloring composition (RG-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).
PG58 green composition (P-7): 31.8 parts PY150 yellow composition (P-8): 18.2 parts Resin solution 1: 7.5 parts Photopolymerizable monomer: 2.0 parts (dipenta Erythritol hexaacrylate)
Photopolymerization initiator: 1.0 part (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF))
Photopolymerization initiator: 0.5 part (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ( “Irgacure OXE02” manufactured by BASF)
Organic solvent: 39.0 parts (ethylene glycol monomethyl ether acetate)

[Example 4-1]
(Color filter (CF-1))
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied on the substrate with a spin coater to form a colored coating. The film was irradiated with ultraviolet rays of 150 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkali developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 220 ° C. for 20 minutes to obtain a red filter segment. Formed. Here, after the heat treatment at 220 ° C., the red filter segment was adjusted to the chromaticity of x = 0.645 and y = 0.323 in the C light source (hereinafter also used for green and blue). Further, by the same method, the green filter segment is adjusted to chromaticity of x = 0.290 and y = 0.600 using the green photosensitive coloring composition (RG-1), and the blue filter segment is Using the photosensitive coloring composition (RB-4) of the present invention so as to match the chromaticity of x = 0.150 and y = 0.060, each filter segment is formed, and the color filter (CF-1) Got.

[Examples 4-1 to 7 and Comparative Examples 4-1 and 2]
(Color filter (CF-2 ~ 9))
Hereinafter, except having changed into the combination of the red photosensitive coloring composition and blue photosensitive coloring composition which are shown in Table 4, the color filter (CF-2-9) was obtained like the color filter (CF-1). .

<Evaluation of color filter>
About the obtained color filter, evaluation regarding the brightness (spectral transmittance) and contrast ratio was performed by the following method. The results are shown in Table 4.

(Brightness (spectral transmittance))
The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. In the evaluation results, “◯” indicates a satisfactory result, and “Δ” corresponds to a level at which there is no problem in use although there are some problems.
○: 28.80 or more Δ: 28.60 or more and less than 28.80 ×: less than 28.60

(Contrast ratio)
Judgment criteria are as follows. In the evaluation results, “◯” indicates a satisfactory result, and “Δ” corresponds to a level at which there is no problem in use although there are some problems.
○: 17500 or more Δ: 16500 or more and less than 17500 ×: less than 16500

  It was confirmed that the color filter including the filter segment formed from the color filter coloring composition containing the color filter colorant of the present invention has high brightness and contrast.

Claims (9)

A color filter coloring composition containing a colorant, a resin, and a solvent,
A coloring composition for a color filter, wherein the colorant contains a xanthene dye (A1) represented by the following general formula (1) and a xanthene dye (A2) having fluorescence.
General formula (1)

[In General Formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Y ₁ is an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent, and 6 carbon atoms which may have a substituent. 10 to 10 aryl groups or a group represented by the general formula (2). R ₂ and Y ₁ may together form a ring containing a nitrogen atom. T ₁ and T ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₁ is a hydrogen atom, a methyl group or a methoxy group. When the general formula (1) has an acidic group, the acidic group may be salted with a resin Z ⁺ having a cationic group in the side chain. ]

General formula (2)

[In General Formula (2), T ₃ and T ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₂ is a hydrogen atom, a methyl group or a methoxy group. * Represents a linking site. When the general formula (2) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ] The colored composition for a color filter according to claim 1, wherein the xanthene dye (A1) is a xanthene dye (A1 ') represented by the following general formula (3).
General formula (3)

[In General Formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Y ₂ is an alkyl group having 1 to 10 carbon atoms that may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms that may have a substituent, or 6 carbon atoms that may have a substituent. Represents 10 to 10 aryl groups. R ₄ and Y ₂ may together form a ring containing a nitrogen atom. T ₅ and T ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. W ₃ is a hydrogen atom, a methyl group or a methoxy group. When the general formula (3) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ] The content of the xanthene dye (A1) is 0.1% by mass to 10.0% by mass with respect to the total of the xanthene dye (A1) represented by the general formula (1) and the xanthene dye (A2) having fluorescence. The coloring composition for a color filter according to claim 1 or 2. The coloring for a color filter according to any one of claims 1 to 3, wherein the xanthene dye (A1) represented by the general formula (1) is a salt-forming compound with a resin Z ⁺ having a cationic group in a side chain. Composition. The colored composition for a color filter according to any one of claims 1 to 4, wherein the xanthene dye (A2) having fluorescence is a salt-forming compound of a xanthene acidic dye and a resin Z ⁺ having a cationic group in a side chain. . The coloring composition for a color filter according to any one of claims 1 to 5, wherein the colorant further contains an organic pigment. Furthermore, the coloring composition for color filters of any one of Claims 1-6 containing at least one of a photopolymerizable monomer and a photoinitiator. The color filter formed with the coloring composition for color filters of any one of Claims 1-7. A colorant for a color filter containing a xanthene dye (A1 ′) represented by the following general formula (3).
General formula (3)

[In General Formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. T ₅ and T ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent. Y ₂ is an alkyl group having 1 to 10 carbon atoms that may have a substituent, a cycloalkyl group having 5 to 8 carbon atoms that may have a substituent, or 6 carbon atoms that may have a substituent. Represents 10 to 10 aryl groups. R ₄ and Y ₂ may together form a ring containing a nitrogen atom. W ₃ is a hydrogen atom, a methyl group or a methoxy group. When the general formula (3) has an acidic group, the acidic group may be salted with the resin Z ⁺ having a cationic group in the side chain. ]