JP6911604B2 - Colorants for color filters, coloring compositions for color filters, and color filters - Google Patents

Description

The present invention includes a colorant for a color filter used for manufacturing a color filter used for manufacturing a color liquid crystal display device, a color image pickup tube element, and the like, a coloring composition for a color filter, and a filter segment formed by using these. It is about the color filter to be used.

In color filter applications, dye-based colorants are attracting attention in order to achieve high contrast ratio and high brightness that cannot be achieved with pigments. Among them, xanthene dyes such as rhodamine dyes and eosin dyes are expected as materials for achieving high brightness because they have superior color characteristics.

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

As described above, a color filter compatible with high brightness and high contrast ratio by the xanthene dye has not been realized.

Japanese Unexamined Patent Publication No. 2012-194523 Japanese Unexamined Patent Publication No. 2013-101166 Japanese Unexamined Patent Publication No. 2014-215515

An object of the present invention is to provide a coloring composition for a color filter, which enables the production of a color filter having a high brightness and a high contrast ratio. Another object of the present invention is to provide a color filter having a high brightness and a high contrast ratio using the coloring composition for a color filter. Further, an object of the present invention is to provide a colorant for a color filter, which has less fluorescent light emission and is excellent in color characteristics when used as a colorant.

As a result of diligent research to solve the above problems, the present inventor has found a coloring composition for a color filter containing a specific xanthene dye (A1) having a benzimidazolone group and a xanthene dye (A2) having fluorescence. It has been found that the fluorescence quenching effect of the xanthene dye (A1) can improve the decrease in contrast ratio and achieve high brightness and high contrast ratio, and the present invention has been made based on this finding.

That is, the present invention is a coloring composition for a color filter containing a coloring agent, a resin, and a solvent, wherein the coloring agent has a xanthene dye (A1) represented by the following general formula (1) and xanthene having fluorescence. The present invention relates to a coloring composition for a color filter containing a dye (A2).

［一般式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｙ_１は、置換基を有してもよい炭素数１〜１０のアルキル基、置換基を有してもよい炭素数５〜８のシクロアルキル基、置換基を有してもよい炭素数６〜１０のアリール基又は一般式（２）で表される基を表す。Ｒ_２及びＹ_１は、一緒になって窒素原子を含む環を形成してもよい。Ｔ_１及びＴ_２は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｗ_１は、水素原子、メチル基又はメトキシ基である。一般式（１）が酸性基を有する場合、その酸性基は、側鎖にカチオン性基を有する樹脂Ｚ^＋と造塩してもよい。］ General formula (1)

[In the general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. Y ₁ has 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. Represents an aryl group of 10 or a group represented by the general formula (2). R ₂ and Y ₁ may be combined to form a ring containing a nitrogen atom. T ₁ and T ₂ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or 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 salt-formed ^{with resin Z + having a cationic group in the side chain.} ]

［一般式（２）中、Ｔ_３及びＴ_４は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｗ_２は、水素原子、メチル基又はメトキシ基である。＊は連結部位を表す。一般式（２）が酸性基を有する場合、その酸性基は、側鎖にカチオン性基を有する樹脂Ｚ^＋と造塩してもよい。］ General formula (2)

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

［一般式（３）中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｙ_２は、置換基を有してもよい炭素数１〜１０のアルキル基、置換基を有してもよい炭素数５〜８のシクロアルキル基又は置換基を有してもよい炭素数６〜１０のアリール基を表す。Ｒ_４及びＹ_２は、一緒になって窒素原子を含む環を形成してもよい。Ｔ_５及びＴ_６は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｗ_３は、水素原子、メチル基又はメトキシ基である。一般式（３）が酸性基を有する場合、その酸性基は、側鎖にカチオン性基を有する樹脂Ｚ^＋と造塩してもよい。］ The present invention also relates to the above-mentioned coloring composition for a color filter, wherein the xanthene dye (A1) is a xanthene dye (A1') represented by the following general formula (3).
General formula (3)

[In the general formula (3), R ₃ and R ₄ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. Y ₂ may have 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, or 6 carbon atoms which may have a substituent. Represents 10 to 10 aryl groups. R ₄ and Y ₂ may be combined to form a ring containing a nitrogen atom. T ₅ and T ₆ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or 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 resin Z + having a cationic group in the side chain.} ]

Further, in the present invention, the content of the xanthene dye (A1) is 0.1% by mass to 10% 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 present invention relates to the above-mentioned coloring composition for a color filter, which is 0% by mass.

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

The present invention also relates to the above-mentioned coloring composition for a color filter, in which the coloring agent further contains an organic pigment.

The present invention further relates to the above-mentioned coloring composition for a color filter, which contains at least one of a photopolymerizable monomer and a photopolymerization initiator.

The present invention also relates to a color filter formed by the above-mentioned coloring composition for a color filter.

［一般式（３）中、Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｔ_５及びＴ_６は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｙ_２は、置換基を有してもよい炭素数１〜１０のアルキル基、置換基を有してもよい炭素数５〜８のシクロアルキル基又は置換基を有してもよい炭素数６〜１０のアリール基を表す。Ｒ_４及びＹ_２は、一緒になって窒素原子を含む環を形成してもよい。Ｗ_３は、水素原子、メチル基又はメトキシ基である。一般式（３）が酸性基を有する場合、その酸性基は、側鎖にカチオン性基を有する樹脂Ｚ^＋と造塩してもよい。］ Further, the present invention relates to a colorant for a color filter containing a xanthene dye (A1') represented by the following general formula (3).
General formula (3)

[In the general formula (3), R ₃ and R ₄ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. T ₅ and T ₆ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. Y ₂ may have 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, or 6 carbon atoms which may have a substituent. Represents 10 to 10 aryl groups. R ₄ and Y ₂ may be combined to 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 resin Z + having a cationic group in the side chain.} ]

INDUSTRIAL APPLICABILITY According to the present invention, a coloring composition for a color filter, which improves the decrease 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. It is possible to provide a color filter using a color composition for a color filter and a colorant for a color filter having less fluorescent light emission and having excellent color characteristics when used as a colorant.

The coloring composition for a color filter of the present invention is a color filter containing a xanthene dye (A1) represented by the general formula (1), a colorant containing a fluorescent xanthene dye (A2), a resin, and a solvent. Coloring composition for use. Hereinafter, various constituent components of the coloring composition for a color filter of the present invention will be described. In addition, in this specification, when it is described as "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide", it is referred to as "(meth) acrylamide". Unless otherwise stated, "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylic acid", 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 contains a xanthene dye (A1) represented by the general formula (1) and a xanthene dye (A2) having fluorescence as a colorant to achieve 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 is improved.

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

［一般式（１）中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｙ_１は、置換基を有してもよい炭素数１〜１０のアルキル基、置換基を有してもよい炭素数５〜８のシクロアルキル基、置換基を有してもよい炭素数６〜１０のアリール基又は一般式（２）で表される基を表す。Ｒ_２及びＹ_１は、一緒になって窒素原子を含む環を形成してもよい。Ｔ_１及びＴ_２は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｗ_１は、水素原子、メチル基又はメトキシ基である。一般式（１）が酸性基を有する場合、その酸性基は、側鎖にカチオン性基を有する樹脂Ｚ^＋と造塩してもよい。］ General formula (1)

[In the general formula (1), R ₁ and R ₂ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent. Y ₁ has 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. Represents an aryl group of 10 or a group represented by the general formula (2). R ₂ and Y ₁ may be combined to form a ring containing a nitrogen atom. T ₁ and T ₂ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or 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 salt-formed ^{with resin Z + having a cationic group in the side chain.} ]

［一般式（２）中、Ｔ_３及びＴ_４は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。Ｗ_２は、水素原子、メチル基又はメトキシ基である。＊は連結部位を表す。一般式（２）が酸性基を有する場合、その酸性基は、側鎖にカチオン性基を有する樹脂Ｚ^＋と造塩してもよい。］ General formula (2)

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

The alkyl groups 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 and 2 -In addition to linear or branched alkyl groups such as ethylhexyl groups, 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 substituents such as hydroxy group and sulfo group. ..

An alkyl group having 1 to 10 carbon atoms which may have a substituent in Y ₁ is synonymous with an 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 which may have a substituent in Y ₁ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. An unsubstituted cycloalkyl group having 5 to 8 carbon atoms 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, as well as a p-methylphenyl group, a p-bromophenyl group and a 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- Examples thereof include a 2,6-dimethylphenyl group and a 2-methoxy-5-sulfophenyl group. Of 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- Bromo-2,6-dimethylphenyl group, 4-sulfo-2,6-dimethylphenyl group and 2-methoxy-5-sulfophenyl group are more preferable.

Alkyl groups having 1 to 10 carbon atoms in T _{1 to} T ₄ are synonymous with alkyl groups having 1 to 10 carbon atoms in _{R 1} and R _2.

Further, 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 used as substituents, which are -SO ₃ H; -COOH; and one of these acidic groups. It may have a valent to trivalent metal salt or alkylammonium salt, −SO ₃ ⁻ Z ⁺ , or CO ₂ ⁻ Z ^+. Z ⁺ represents a resin having a cationic group in the side chain.

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

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

When R ₂ and Y ₁ are combined to form a ring containing a nitrogen atom, the formed ring may have a substituent. As the substituent for example, a methyl group, an ethyl group, a chlorine atom, -COOH, -OH, -SO ₃ H and the like, -COOH, -OH, -SO ₃ H 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. Above all, it is preferable that R ₂ and Y ₁ are combined to form a 6-membered ring containing a nitrogen atom.

As R ₁ and R ₂ , an alkyl group having 1 to 10 carbon atoms which is unsubstituted or having a sulfo group is preferable, an alkyl group having 1 to 5 carbon atoms which is unsubstituted is more preferable, and a propyl group is particularly preferable. As T ₁ and T ₂ , a hydrogen atom or an unsubstituted alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom, a propyl group or a butyl group is more preferable. As Y ₁ , 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 is preferable, 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 further 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. ^{When the substituent has an acidic group, it is preferably a salt-forming compound with resin Z +} having a cationic group in the side chain, and the acidic group is preferably a sulfo group. Hydrogen atoms are preferable as W ₁ and W _2.

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

［一般式（３）中、
Ｒ_３及びＲ_４は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。
Ｙ_２は、置換基を有してもよい炭素数１〜１０のアルキル基、置換基を有してもよい炭素数５〜８のシクロアルキル基又は置換基を有してもよい炭素数６〜１０のアリール基を表す。
Ｒ_４及びＹ_２は、一緒になって窒素原子を含む環を形成してもよい。
Ｔ_５及びＴ_６は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜１０のアルキル基を表す。
Ｗ_３は、水素原子、メチル基又はメトキシ基である。
一般式（３）が酸性基を有する場合、その酸性基は、側鎖にカチオン性基を有する樹脂Ｚ^＋と造塩してもよい。］ General formula (3)

[In general formula (3),
R ₃ and R ₄ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent.
Y ₂ may have 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, or 6 carbon atoms which may have a substituent. Represents 10 to 10 aryl groups.
R ₄ and Y ₂ may be combined to form a ring containing a nitrogen atom.
T ₅ and T ₆ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or 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 resin Z + having a cationic group in the side chain.} ]

In the general formula (3), it may have 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 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 has the same meaning as the description 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 suitable onium salt structure is available from the viewpoint of availability and the like. , Ammonium salt, iodonium salt, sulfonium salt, diazonium salt, and phosphonium salt, and in consideration of storage stability (thermal stability), ammonium salt, iodonium salt, and sulfonium salt are more preferable. More preferably, it is an ammonium salt. The xanthene dye (A1) represented by the general formula (1) and the xanthene dye (A2) having fluorescence are preferably salt-forming compounds ^{with resin Z + having a cationic group in the side chain.}

(Acrylic resin containing a structural unit represented by the general formula (4))
^{It is desirable that the resin Z +} having a cationic group in the side chain is the same as the resin constituting the coloring composition for a color filter. Since an acrylic resin is preferably used as the resin, Z ⁺ is preferably an acrylic resin, and an acrylic resin containing a structural unit represented by the following general formula (4) is more preferable.

General formula (4)

[In the general formula (4), R ₂₁ represents a hydrogen atom or an alkyl group which may have a substituent. R _{22 to} R ₂₄ independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent. Two of R _{22 to} R ₂₄ may be combined with 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 in 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, a cyclohexyl group and the like. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly 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 them, the R _21, a hydrogen atom or a methyl group is most preferable.

Examples of the alkyl group in R _{22 to} R ₂₄ include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, etc. 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, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and crosslinked cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As the alkyl group, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.

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-pro. Penyl, etc.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.) can be mentioned. As the alkenyl group, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 8 carbon atoms is more preferable.

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

When the _{alkyl group, alkenyl group, and aryl group represented by R 22 to} R ₂₄ have a substituent, the substituent includes, for example, a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, and the like. Examples thereof include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group and the like. As the substituent, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable. As R _{22 to} R ₂₄ , an alkyl group is preferable from the viewpoint of stability and the like, and an unsubstituted alkyl group is particularly preferable.

In the general formula (4), the Q connecting the acrylic sites and ammonium salt, an alkylene group, an arylene _{group, -CONH-R 25 -, -} COO-R 25 - represents an alkylene group and arylene _{group, R 22} a hydrogen atom from an alkyl group and an aryl group in to R ₂₄ is one group formed by removing. Among them, the polymerizable, for reasons of _{availability, -CONHR 25 -, - COO-} R 25 - is preferably. Further, it is more preferable that R ₂₅ is a methylene group, an ethylene group, a propylene group, or a butylene group, and it is particularly preferable that it is 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 adopted without limitation, and specifically, hydroxide ion; halogen ion such as chloride ion, bromide ion and iodide ion; carboxylate ion such as formate ion and acetate ion; carbon dioxide. Complexes such as ions, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, permanganate ion, and even hexacyanoferrate (III) acid ion. Ions and the like can be mentioned. From the viewpoint of synthetic suitability and stability, halogen ions and carboxylic acid ions are preferable, and halogen ions are most preferable. When the anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion may be covalently bonded to the resin to form an intramolecular salt.

In order to obtain an acrylic resin containing a 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 is used. A monomer component containing an ethylenically unsaturated monomer may be copolymerized to obtain an acrylic resin having an amino group, and then an onium chloride agent may be reacted to obtain ammonium chloride.

Specific examples of the ethylenically unsaturated monomer having an ammonium base, the ethylenically unsaturated monomer having an amino group, other copolymerizable ethylenically unsaturated monomer, and the onium chloride agent are described below. Although shown, the present invention is not limited to these, and known ones can be used endlessly.

(Ethylene 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-based quaternary ammonium salts such as oxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloyl amide-based quaternary ammonium salt, dimethyldialylammonium methylsulfate, trimethylvinylphenylammonium chloride and the like can be mentioned.

(Ethylene 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, dit-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl (Meta) acrylic acid ester or (meth) having a dialkylamino group such as aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, dit-butylaminopropyl (meth) acrylamide, etc. Examples include acrylamide, styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylamine compounds such as diallylmethylamine and diallylamine, and amino such as N-vinylpyrrolidin, N-vinylpyrrolidone and N-vinylcarbazole. Group-containing aromatic vinyl-based monomers can be mentioned.

(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, and itaconic acid diesters. Examples thereof include (meth) acrylamides, vinyl ethers, esters of vinyl alcohols, styrenes, and (meth) acrylonitrile.

Since the acrylic resin containing the structural unit represented by the general formula (4) preferably has a heat-crosslinkable functional group in order to improve the resistance of the coating film, other copolymerizable ethylenically unsaturated monomers. The mer is preferably a monomer having a crosslinkable functional group. The suitable structure of the thermally crosslinkable functional group is not particularly limited, but for example, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride, an imino group, an oxetanyl group, a t-butyl group, an epoxy group, a mercapto group and an isocyanate group (block). (Including isocyanate group), allyl group, (meth) acrylic group and the like. Of these, a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, and a (meth) acrylic group are preferable 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, and a t-butyl group are more preferable.

Two or more types of thermally crosslinkable functional groups may be contained. 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 preferable.

Further, 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. Acrylic resins having a glass transition temperature (hereinafter abbreviated as Tg) of 50 ° C. or higher form a stronger film in the heating process in the manufacture of color filters, preventing color change of the coating film, that is, improving heat resistance. Also, the solvent resistance is improved.

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

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. Is more preferable.

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. It is preferably 3,000 to 15,000, more preferably 3,000 to 15,000.

In the resin having a cationic group in the side chain, the total content of the structural units represented by the above 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 above general formula (4) is 5% by weight or more from the viewpoint of solvent solubility and coloring power of the salt-forming compound. It is preferably 10 to 50% by weight, more preferably 10 to 50% by weight.

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

In the reaction between an ethylenically unsaturated monomer having an amino group and an onium chloride agent, an onium chloride agent having an equimolar amount or less with respect to the amino group is usually added dropwise to an ethylenically unsaturated monomer solution having an amino group. Can be done by doing. The temperature during the ammonium chlorination reaction is about 90 ° C. or lower, and particularly when the vinyl monomer is ammonium chlorinated, the temperature is preferably about 30 ° C. or lower, and the reaction time is about 1 to 4 hours.

As the 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 glycol 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, tetraflufuryl 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, most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

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

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

Specific examples of the xanthene dye A1 of the present invention include, but are not limited to, the xanthene dyes (XA1) to (XA24) shown below, salt-forming compounds of the dye, and the like.

<Fluorescent xanthene dye (A2)>
The xanthene dye (A2) having fluorescence is not particularly limited as long as it has fluorescence, but a xanthene oil-soluble dye, a xanthene basic dye, and a xanthene acid dye are preferably used. Among them, in the transmittance 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 650 nm region, the transmittance is 80% or more in the 600 nm region, the transmittance is 10% or less in the 500 to 550 nm region, and the transmittance is 75% in the 400 nm region. That is all.

[Xanthene oil-soluble dye]
Examples of xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and 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 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, and CI Solvent Red, which are rhodamine-based oil-soluble dyes with high color development. Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferred.

[Xanthene basic dye]
Examples of the xanthene basic dye include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic Violet 10 (Rhodamine B) and the like can be mentioned. Among them, C.I. I. Basic Red 1, C.I. I. It is preferable to use Basic Violet 10.

[Xanthene acid dye]
The acid dye of the xanthene dye will be described. Examples of the acid dye of the xanthene dye include C.I. I. Acid Red 51 (erythrosine (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 Phloxine 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. It is preferable to use acid violet 30 and those represented by the following general formula (5). Among these, C.I., a rhodamine-based acid dye, is particularly excellent in color development, heat resistance, and light resistance. I. It is preferable to use Acid Red 52 or the one represented by the following general formula (5) (CI Acid Red 289 or the like), and among them, the one represented by the general formula (5) is particularly preferable.

General formula (5)

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

In the general formula (5), it may have 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 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 has the same meaning as the description of the general formulas (1) and (2).

R ₅ and R ₆ are preferably an alkyl group having 1 to 5 carbon atoms which may have a hydrogen atom or a substituent, 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, and have 1 to 1 unsubstituted carbon atoms. An aryl group having 6 to 10 carbon atoms which may have an alkyl group of 5 or a substituent is preferable, and an alkyl group having 1 to 5 carbon atoms substituted with sulfonic acid is particularly preferable.

As the xanthene dye (A2) having fluorescence, a xanthene basic dye and a xanthene acid dye are preferable, and they can also be used as a salt-forming compound or a sulfonic acid amide compound. The xanthene basic dye is preferably used by chlorinating with an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Of these, it is preferable to use naphthalene sulfonic acid such as tobias acid or perchloric acid in terms of resistance. Further, the xanthene acid dye is preferably used as a salt-forming compound by salt-forming with a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, and a resin component having a functional group thereof. .. ^{As the resin component, the resin Z +} having a cationic group in the side chain described above is preferably used. Of these, a salt-forming compound of a xanthene acid 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, preferably 0.5% by mass to 5% by mass, based on the total of the xanthene dye (A1) and the fluorescent xanthene dye (A2). .0% by mass is more preferable. When the xanthene dye is used as the salt-forming compound, the resin portion is not included in the content of the xanthene dye.

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

[Organic pigment]
Examples of the blue pigment 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 can be mentioned. 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, more preferably C.I. I. Pigment Blue 15: 6.

In particular, when the coloring composition is used for a blue filter segment, by using a blue pigment in combination, the spectral spectrum can have a high transmittance in the vicinity of 425 to 500 nm, which has a characteristic peak of many backlights. It is possible, and it is preferable because a higher brightness can be obtained as a blue filter segment than a colorant in which a conventional blue pigment and other pigments are combined.

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, Japanese Patent Application Laid-Open No. 2008-19383 Examples thereof include zinc phthalocyanine pigments described in JP-A-2007-320986, JP-A-2004-070342, 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, it is preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment described in Japanese Patent Application Laid-Open No. 2004-333817, Japanese Patent No. 4893859, etc. can also be used.

Examples of the yellow pigment 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, 173, 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 can be mentioned. 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 the purple pigment 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 can be mentioned. 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 the red pigment 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, 179, 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 Special Table 2011-523433. Examples thereof include diketopyrrolopyrrole pigments described in the publication.

Examples of the orange pigment that works in the same manner as the red pigment include C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61 and other orange pigments 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 preferred to use Pigment Red 177.

(Pigment miniaturization)
When the colorant used in combination with the coloring composition of the present invention is a pigment, it can be made finer by a salt milling treatment or the like. The average primary particle size determined by the TEM (transmission electron microscope) of the pigment is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 90 nm, sufficient spectral characteristics may not be obtained. For this reason, the more preferable average primary particle size is in the range of 10 to 70 nm.

Salt milling treatment is a kneading of a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent with a needle, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, or the like. This is a process 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 acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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 price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment.

The water-soluble organic solvent has a function of wetting 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethaneol, 2- (isopentyloxy) etanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. Tel, Triethylene Glycol, Triethylene Glycol Monomethyl Ether, Liquid Polyethylene Glycol, 1-Methoxy-2-Propylene, 1-ethoxy-2-Propylene, Dipropylene Glycol, Di 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, most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, 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 coloring composition for a color filter. This range is preferable because the color reproducibility is good when the color filter is used in a general film thickness range (about 1.0 to 3.0 μm).

[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 thereof include quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acrydin dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes.

<Resin>
The resin includes a colorant, particularly a xanthene dye of the present invention, a salt-forming compound thereof and a pigment that disperses the pigment, or a resin that dyes and permeates them, and examples thereof include a thermoplastic resin and a thermosetting resin. The spectral transmittance of the resin in the entire wavelength region of 400 to 700 nm in the visible light region 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 resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin 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.

When the coloring composition for a color filter of the present invention is used in the form of an alkali-developable colored resist material, an alkali-soluble resin is preferably used, and an alkali-soluble copolymer of an acidic group-containing ethylenically unsaturated monomer is copolymerized. 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 a resin having an acidic group such as a carboxyl group and a sulfone group. Specifically, as the alkali-soluble resin, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (maleic anhydride) maleic anhydride copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic group and at least one resin selected from 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 ethylenically unsaturated monomer, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used. Further, 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 a resin in which an unsaturated ethylenically double bond is introduced by the methods (a) and (b) shown below.

[Method (a)]
As the method (a), for example, the side chain epoxy group of the copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other types of monomers can be used. , The carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenically double bond is added and reacted, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenically double bond and a carboxyl group. There is a way to introduce it.

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

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic dianhydride such as pyromellitic acid dianhydride may be used to obtain the remaining anhydride. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically double bond can be further 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 with one or more other monomers. There is a method of introducing an unsaturated ethylenically double bond and a carboxyl group by adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl groups.

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

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 and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited to these. However, two or more types can be used together.

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

From the viewpoints of dispersibility, permeability, developability, and heat resistance of pigments and salt-forming compounds, the resin has an affinity for a colorant adsorbent group, a carboxyl group that acts as an alkali-soluble group during development, a colorant carrier, and a solvent. The balance of aliphatic and aromatic groups acting as a group is important for the dispersibility, permeability, developability, and durability of pigments and salt-forming compounds, and a resin having an acid value of 20 to 300 mgKOH / g should be used. Is preferable. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If 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 forming property and various resistances, and has a high colorant concentration and can exhibit good color characteristics. Therefore, it is preferable to use it 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 into the colorant carrier, and the filter segment is applied onto 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, and the like. 2-Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanol, 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-dimethylformamide, 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 monotersial 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 Monoethyl 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, methyl isobutyl ketone, methyl cyclo Examples thereof include hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester.

Among them, 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 have good dispersion and dissolution of the colorant of the present invention. , 3-methoxybutanol, alcohols such as benzyl alcohol and ketones such as cyclohexanone are preferably used. 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 may be used alone or in admixture of two or more. When two or more kinds of mixed solvents are used, it is preferable that the above-mentioned preferable organic solvent is contained in an amount of 65 to 95% by weight.

Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, 800 to 4000 weight based on the total weight of the colorant (100% by weight). It is preferable to use it in an amount of%.

<Dispersion>
When the coloring composition of the present invention contains a pigment, it is finely divided by using various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor, preferably together with a dispersion aid such as a dye derivative. Can be dispersed and manufactured. Further, the coloring composition of the present invention can also be produced by mixing xanthene dyes, other coloring agents and the like separately dispersed in a coloring agent carrier.

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

(Dye derivative)
Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent. Those described in Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used, and these can be used. It can be used alone or in combination of two or more.

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

(Resin type dispersant)
The resin-type dispersant has a pigment-affinitive moiety having a property of adsorbing to the additive pigment and a moiety compatible with the colorant carrier, and adsorbs to the additive pigment to stabilize the dispersion on the colorant carrier. It works. Specifically, as the resin type dispersant, 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 of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by BASF Japan Limited. , 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- P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, manufactured by Lubrizol Japan, Inc. 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, manufactured by BASF Japan Ltd. 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451 and 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. And so on.

As the polyester-based dispersant, dispersants produced by known methods described in WO2008 / 007776, JP2009-155406, and JP2010-185934 can be used.

(Surfactant)
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When the resin type dispersant and the surfactant are added, the blending amount 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). 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 effect of addition, and when the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Photopolymerizable monomer>
The coloring composition of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer of the present invention contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like 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 ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

<Photopolymerization initiator>
The coloring composition for a color filter of the present invention is a solvent-developed or alkali-developed colored resist material to which a photopolymerization initiator or the like is added when the composition is cured by ultraviolet irradiation to form a filter segment by a photolithography method. It can be prepared in the form of. When the photopolymerization initiator is used, the blending amount is preferably 5 to 200% by weight based on the total amount of the colorant, and is 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-. Hydroxycyclohexylphenylketone, 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) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone or 2,4-diethylthioxanthone; 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- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1- (N-4-benzoylphenyl-carbazole-3-yl) -butane-1,2-dione -2-Oxime-O-acetate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-) Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene ) Oxime ester compounds such as hydroxylamine; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9,10-phenanthrene Kinone-based compounds such as quinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanosen-based compounds are used.

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

<Sensitizer>
Further, the coloring composition for a color filter of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglioxylate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the coloring composition (100% by weight), and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes 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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane 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 to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenol-based resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds and the like are effective, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. 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 amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-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.) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by weight based on the total amount of the thermosetting resin.

<Other additive ingredients>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. 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).

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-Epylcyclohexyl) ethyltrimethoxysilane, β- (3,4-epylcyclohexyl) methyltrimethoxysilane, β- (3,4-epylcyclohexyl) ethyltriethoxysilane, β- (3,4-epylcyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as 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 coloring composition of the present invention was mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, by means such as centrifugation, sintering filter, and membrane filter. It is preferable to remove dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a filter segment formed by using the coloring composition for a color filter of the present invention. Examples of the color filter include those including a red filter segment, a green filter segment, and a blue filter segment, or those including a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

As the transparent substrate, a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminum borosilicate glass, or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate is used. Further, 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 for driving the liquid crystal after the panelization.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by the printing method can be patterned simply by repeating printing and drying of the coloring composition prepared as the printing ink, so that the color filter manufacturing method is low cost and excellent in mass productivity. There is. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, it is also possible to perform ultraviolet exposure.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above methods, but the coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, 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 the filter segment is transferred to a desired substrate.

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

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

<Identification of xanthene pigment>
Xanthene dyes were identified by mass spectrometry.
<< Mass Spectrometry >> The analysis was performed using LC; Agilent 1200 type and MASS; Agilent LC / MSD type.

<Manufacturing of resin solution>
(Resin solution 1)
70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube was used. 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 Toa Synthetic Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate is added to the previously synthesized resin solution so that the non-volatile content is 20% by weight. Addition was made 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 placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C., the inside of the flask was replaced with nitrogen, and then methacrylic acid was added from the dropping tube. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic 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 dropping, the reaction was continued for another 3 hours to obtain a copolymer solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karens manufactured by Showa Denko Co., Ltd.). A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. Approximately 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20% by weight to make an alkali-soluble resin solution. 2 was prepared. The weight average molecular weight (Mw) was 18,000.

(Resin solution 3)
123 g of cyclohexanone was introduced into a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the atmosphere inside the flask was changed from air to nitrogen, the temperature was raised to 100 ° C., and then benzyl methacrylate was used. 72.6 g (0.41 mol), 42.0 g (0.49 mol) of methacrylic acid, 23.0 g (0.10 mol) of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 137 g of cyclohexanone was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was continued at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 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 placed in the flask, and the reaction was continued at 110 ° C. for 6 hours. Approximately 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20% by weight to make an alkali-soluble resin solution. 3 was prepared. The weight average molecular weight (Mw) was 10,500.

(Resin solution 4)
370 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C. Milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, 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 was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently 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 and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. An alkali-soluble resin solution 4 was prepared. The weight average molecular weight (Mw) was 19,000.

<Preparation of resin type dispersant solution>
(Resin type dispersant solution 1)
A resin-type dispersant solution 1 having a non-volatile 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 type 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 was 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, and t-butyl were cooled. 16.0 parts of acrylate, 10.0 parts of hydroxymethyl methacrylate and 2.0 parts of ethyl acrylate were charged, 0.10 part of AIBN and 60.0 parts of PGMAc were added, and the reaction was carried out for 10 hours. The solid content measurement confirmed that the polymerization had proceeded by 95%, and the reaction was terminated. 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 15,000.

<Manufacture of ^{resin Z +} having a cationic group in the side chain>
(Resin 1 having a cationic group in the side chain)
67.3 parts of methyl ethyl ketone was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised 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) ) Was made uniform in 6.5 parts and 25.1 parts of methyl ethyl ketone, charged in a dropping funnel, attached to a four-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6,830, and then the mixture was cooled to 50 ° C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added to this solution, and the mixture was reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. In this way, a resin 1 solution having a cationic group in the side chain containing 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 obtained by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converting it 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)
62.4 parts of isopropyl alcohol was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised 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) ) Was made uniform in 5.7 parts and 15.6 parts of methyl ethyl ketone, charged in a dropping funnel, attached to a four-neck separable flask, and added dropwise over 2 hours. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7,420, and then the mixture was 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 having a resin component of 40% by weight. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Resin 3 having a cationic group in the side chain)
82.0 parts of methyl ethyl ketone was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised 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, and Kayama PM-21 (manufactured by Nippon Kayaku Co., Ltd., phosphoric acid ester of 2-hydroxyethyl methacrylate with 1 mol of ε-caprolacron). ), 10.0 parts, diethylaminopropyl methacrylate (17.5 parts), 2,2'-azobis (2,4-dimethylvaleronitrile) (6.0 parts), and methyl ethyl ketone (25.6 parts). It was placed in a 4-neck separable flask and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7,010, and then the mixture was cooled to 50 ° C. In this way, a resin 3 solution having a cationic group in the side chain containing 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 the potentiometric titration method using a 0.1 N hydrochloric acid aqueous solution, and then converted to the equivalent of potassium hydroxide.

(Resin 4 having a cationic group in the side chain)
62.4 parts of isopropyl alcohol was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised 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. , 5.7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 15.6 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a four-neck separable flask, and used for 2 hours. Dropped over. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7,420, and then the mixture was cooled to 50 ° C. 72 parts of isopropyl alcohol was added to this solution to obtain a resin 4 solution in which the resin component had a cationic group in the side chain of 40% by weight. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Resin 5 having a cationic group in the side chain)
62.4 parts of isopropyl alcohol was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised 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 homogenizing 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 5.7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), and 15.6 parts of methylethylketone, the mixture was charged into a dropping funnel, and 4 It was attached to a separable flask and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7,420, and then the mixture was 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 having a resin component of 40% by weight. 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-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 2.5 parts of methacrylic acid, 15.0 parts of 3- (acryloyloxymethyl) 3-methyloxetane, and 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 to replace the inside of the system 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 the 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 rate was 98% or more in terms of the non-volatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 17.7 parts of methacryloylaminopropyltrimethylammonium chloride as a second block monomer were added to this reactor, and the mixture was stirred while maintaining a nitrogen atmosphere at 100 ° C. for the reaction. Continued. Two hours after the addition of the dimethylaminoethylmethyl chloride salt methacrylate, the polymerization solution was sampled and the solid content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction was carried out. The solution was cooled to room temperature to terminate the polymerization. As a result of GPC measurement, the polymer was Mw 9,200 and Mw / Mn = 1.5, and the reaction conversion rate was 98.5%. In this way, a resin 6 having a cationic group in a block-type side chain having a quaternary ammonium salt value of 45 mgKOH / g per solid content was obtained. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether is added so that the non-volatile content becomes 40% by weight to form a block type. A solution of resin 6 having a cationic group in the side chain was obtained.

<Manufacturing of xanthene dye (A1) 1>
[Example 1-1] (Xanthene dye (XA1))
20 mmol of the compound represented by the formula (6) and 80 mmol of 5-amino-2-benzoimidazolinone were added to 50 g of N-methylpyrrolidone, and the mixture was 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA1).
However, Example 1-1 is a reference example.

Equation (6)

[Example 1-2]
(Xanthene dye (XA2))
16 mmol of the 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 matter was filtered off, washed with 750 g of water, and dried to obtain a xanthene dye (XA2).
However, Example 1-2 is a reference example.

[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 the mixture was stirred at 80 to 90 ° C. for 2 hours. After 2 hours, 60 mmol of 5-amino-2-benzoimidazolinone 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 separated by filtration, washed with 750 g of water, and dried to obtain a 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 separated by filtration, washed with 750 g of water, and dried to obtain a 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA5).

[Example 1-6]
(Xanthene dye (XA6))
In the synthesis of the xanthene dye (XA4), the xanthene dye (XA6) was obtained by synthesizing in the same manner as in Example 1-4 except that 2-bromoethylmethyl 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 the mixture was stirred at 80 to 90 ° C. for 2 hours. After 2 hours, 60 mmol of 5-amino-6-methyl-2-benzoimidazolinone 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 separated by filtration, 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA7).

[Example 1-8]
(Xanthene dye (XA8))
Similar to Example 1-7 except that 5-amino-6-methoxy-2-benzoimidazolinone was added instead of 5-amino-6-methyl-2-benzoimidazolinone in the synthesis of the xanthene dye (XA7). The xanthene dye (XA8) was obtained by the above-mentioned method.

[Example 1-9]
(Xanthene dye (XA9))
16 mmol of the 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 separated by filtration, washed with 750 g of water, and dried to obtain a 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 the mixture was stirred at 80 to 90 ° C. for 2 hours. After 2 hours, 60 mmol of 5-amino-2-benzoimidazolinone 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 separated by filtration, 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA10).

[Example 1-11]
(Xanthene dye (XA11))
In the synthesis of the xanthene dye (XA4), the 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. ) Was obtained.

[Example 1-12]
(Xanthene dye (XA12))
20 mmol of the compound represented by the formula (6) and 20 mmol of 5-amino-2-benzoimidazolinone were added to 50 g of N-methylpyrrolidone, and the mixture was 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 separated by filtration, 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA12).

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

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

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

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

[Example 1-17]
(Xanthene dye (XA17))
20 mmol of the compound represented by the formula (6) and 20 mmol of 5-amino-2-benzoimidazolinone were added to 50 g of N-methylpyrrolidone, and the mixture was 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA17).

[Example 1-18]
(Xanthene dye (XA18))
16 mmol of the 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA18).

[Example 1-19]
(Xanthene dye (XA19))
In the synthesis of the xanthene dye (XA18), the xanthene dye (XA19) was obtained by synthesizing 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 the 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 separated by filtration, washed with 750 g of water, and dried to obtain a xanthene dye (XA20).

[Example 1-21]
(Xanthene dye (XA21))
In the synthesis of the xanthene dye (XA3), 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. , Xanthene dye (XA21) was obtained.

[Example 1-22]
(Xanthene dye (XA22))
In sulfuric acid mixed with 98% sulfuric acid 11.6g and oleum (SO ₃ content 30%) 3.4 g, slightly over 1 hour xanthene dyes (XA3) 1.0 g obtained in Example 1-3 They were added one by one and stirred as it was at room temperature for 2 hours. The reaction solution was added to 150 g of water to precipitate the dye. The obtained solid matter was filtered off and dried to obtain a xanthene dye (XA22).

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

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

<Production of xanthene dye (A1) 2 (salt-forming compound)>
[Example 1-23-1]
(Xanthene pigment salt product (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 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 prepared by dissolving 10.0 parts of the xanthene dye (XA23) in 100 parts of a 10% methanol aqueous solution was gradually added dropwise to the previously prepared resin solution. After completion of the dropping, the reaction was carried out by stirring at 30 ° C. for 90 minutes. As the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. After allowing to cool 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 water with a dryer, and 35.3 parts of the salt-forming compound (XA23-) is dried. c1) was obtained. The content of the active dye component derived from the xanthene dye (XA23) in the obtained salt-forming compound (XA23-c1) was 25% by mass.

[Examples 1-23-2]
(Xanthene pigment salt product (XA23-c2))
A solution of resin 2 having a cationic group in the side chain of 44 parts was added to 1500 parts of a 10% aqueous solution of methanol, 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 prepared by dissolving 10.0 parts of the xanthene dye (XA23) in 100 parts of a 10% methanol aqueous solution was gradually added dropwise to the previously prepared resin solution. After completion of the dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. As the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. After allowing to cool 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 water with a dryer to dry 21.6 parts of the salt-forming compound (XA23). -C2) was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c2) was 24% by mass.

[Examples 1-23-3]
(Xanthene pigment salt product (XA23-c3))
A solution of resin 3 having a cationic group in the side chain of 63.2 parts was added to 2000 parts of 20% acetic acid, and after sufficient stirring and mixing, the mixture was heated to 60 ° C. to form a tertiary amino group in the side chain. Ammonium chloride was performed. On the other hand, an aqueous solution prepared by dissolving 10.0 parts of the xanthene dye (XA23) in 90 parts of water was gradually added dropwise to the ammonium chloride resin solution. After completion of the dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. As the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. After allowing to cool 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 water with a dryer, and 39 parts of the salt-forming compound (XA23-c3) is dried. ) Was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c3) was 25% by mass.

[Examples 1-23-4]
(Xanthene pigment salt product (XA23-c4))
A solution of the resin 4 having a cationic group in the side chain of 42 parts was added to 1500 parts of a 10% aqueous solution of methanol, 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 prepared by dissolving 10.0 parts of the xanthene dye (XA23) in 100 parts of a 10% methanol aqueous solution was gradually added dropwise to the previously prepared resin solution. After completion of the dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. As the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. After allowing to cool 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 water with a drier to obtain 23 parts of the salt-forming compound (XA23-c4). ) Was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c4) was 25% by mass.

[Example 1-23-5]
(Xanthene pigment salt product (XA23-c5))
A solution of the resin 5 having a cationic group in the side chain of 43 parts was added to 1500 parts of a 10% aqueous solution of methanol, 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 prepared by dissolving 10.0 parts of the xanthene dye (XA23) in 100 parts of a 10% methanol aqueous solution was gradually added dropwise to the previously prepared resin solution. After completion of the dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. As the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. After allowing to cool 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 water with a drier to obtain 25 parts of the salt-forming compound (XA23-c5). ) Was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c5) was 26% by mass.

[Example 1-23-6]
(Xanthene pigment salt product (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 solution of methanol, 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 prepared by dissolving 10.0 parts of the xanthene dye (XA23) in 100 parts of a 10% methanol aqueous solution was gradually added dropwise to the previously prepared resin solution. After completion of the dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. As the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. After allowing to cool 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 water with a drier to obtain 26 parts of the salt-forming compound (XA23-c6). ) Was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA23) in the salt-forming compound (XA23-c6) was 25% by mass.

[Example 1-21-6]
(Xanthene pigment salt product (XA21-c6))
In the synthesis of the xanthene dye (XA23-c6), the xanthene dye compound (XA21-c6) was synthesized in the same manner as in Example 1-23-6 except that (XA21) was added instead of (XA23). ) Was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA21) in the salt-forming compound (XA21-c6) was 25% by mass.

[Example 1-22-6]
(Xanthene pigment salt product (XA22-c6))
In the synthesis of the xanthene dye (XA23-c6), the xanthene dye compound (XA22-c6) was synthesized in the same manner as in Example 1-23-6 except that (XA22) was added instead of (XA23). ) Was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA12) in the salt-forming compound (XA22-c6) was 25% by mass.

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

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

<Manufacturing of fluorescent xanthene dye (A2)>
(Fluorescent xanthene dye (XA33))
C. I. Acid Red 289 16 mmol 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 separated by filtration to obtain them, washed with 800 parts of ethyl acetate, and dried to obtain a xanthene dye (XA33).

Xanthene dye (XA33)

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

(Fluorescent xanthene dye salt product (XA33-c2))
In the synthesis of the xanthene dye (XA23-c2), the xanthene dye (XA33-c2) was synthesized in the same manner as in Example 1-23-2 except that the xanthene dye (XA33) was added instead of the xanthene dye (XA23). ) Was obtained. At this time, the content of the active dye component derived from the xanthene dye (XA33) in the salt-forming compound (XA33-c2) was 25% by mass.

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

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

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

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

(Fluorescent xanthene dye salt product (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 solution of methanol, 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 prepared by dissolving 0.3 parts of xanthene dye (XA23) and 9.7 parts of xanthene dye (XA33) in 100 parts of a 10% methanol aqueous solution is gradually added dropwise to the previously prepared resin solution. did. After completion of the dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. As the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and setting the end point at the point where the bleeding disappeared. After allowing to cool 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 water with a drier to obtain 28 parts of the salt-forming compound (XA23,33). -C6) was obtained. At this time, the content of the active dye component derived from the xanthene dye (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 is stirred and mixed so as to be uniform, and then dispersed for 5 hours 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 part 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 Compositions DA-2 to 58)
Hereinafter, as shown in Table 2, coloring compositions (DA-2 to 58) were obtained in the same manner as the coloring 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 coloring composition (DA-1 to 58) was evaluated by the following method. The results are shown in Table 2.
However, Examples 2-1 and 2-2 are reference examples.

(Contrast ratio)
The coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater so that the film thickness of the dry coating film was 1.2 μm, and the mixture was placed in an oven at 230 ° C. for 20 minutes. A coated substrate was prepared by firing. 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. At the time of measurement, a black mask having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light. The judgment criteria are as follows. In the evaluation results, ◯ is a good result, Δ is a level that has some problems but no problem in use, and × is unsuitable for use.
◯: 10000 or more Δ: 7000 or more and less than 10000 ×: less than 7000

The abbreviations shown in Table 2 are shown below.
(Xanthene dyes (XA31, XA32))

(Parthalocyanine pigment (Compound B))

(Fluorescent cyanine pigment (Compound C))
Similar to the fluorescent dye (A-11) in JP-A-2015-18208, a resin having an anionic group and C.I. I. A fluorescent cyanine dye (Compound C), which is a salt-forming compound with Basic Red 12, was obtained.

The coloring 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) all have an excellent contrast ratio, which is xanthene. It is considered that the effect is that the fluorescence of the xanthene dye (A2) is suppressed by the benzimidazolone group of the dye (A2).

<Manufacturing 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 Toyo Color Co., Ltd., 35.0 parts of resin solution 1, 5 parts of resin type dispersant solution, propylene glycol monomethyl ether acetate After 49 parts were uniformly stirred and mixed, dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then filtered through a 5 μm filter. A blue composition (P-1) was prepared.

[Example 2-53]
(Blue composition (P-2): xanthene dye / PB15: 6)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours 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 prepared by filtering with the filter of.
Xanthene dye (XA23-c6): 0.02 part Fluorescent xanthene dye (XA33-c6): 2.33 part PB15: 6 Pigment: 8.80 part Resin type dispersant solution 1: 4.00 part 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 is stirred and mixed so as to be uniform, and then dispersed for 5 hours 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 prepared by filtering with the filter of.
Fluorescent xanthene dye (XA23,33-c6): 2.35 parts PB15: 6 pigments: 8.80 parts Resin type dispersant solution 1: 4.00 parts Resin solution 1: 30.68 parts Propylene glycol monomethyl ether acetate: 54 .17 copies

[Example 2-55]
(Blue composition (P-4): xanthene dye / PB15: 6)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours 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 prepared by filtering with the filter of.
Fluorescent xanthene dye (XA23,33-c6): 2.35 parts PB15: 6 pigments: 8.80 parts Resin type dispersant solution 2: 4.00 parts Resin solution 1: 30.68 parts Propylene glycol monomethyl ether acetate: 54 .17 copies

(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), but the red composition (P-5) of PR254 was prepared by the same production method as the blue composition (P-1). Made.

(Red composition (P-6): PR177)
C. I. Pigment Blue 15: 6 to C.I. I. A red composition (P-6) of PR177 was prepared by the same production method as the blue composition (P-1) except that it was changed to 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 prepared by the same production method as the blue composition (P-1) except that it was changed to 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 prepared by the same production method as the blue composition (P-1) except that it was changed to Pigment Yellow 150 (PY150) (“E4GN” manufactured by LANXESS).

<Manufacturing of photosensitive coloring compositions for color filters>
[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 Coloring 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 (BASF's "Irgacure 907"))
Photopolymerization Initiator: 0.5 parts (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime) ( BASF "Irgacure OXE02")
Organic solvent: 39.0 parts (propylene glycol monomethyl ether acetate)

[Examples 3-2 to 52, Comparative Examples 3-1 to 6]
(Photosensitive coloring compositions (RB-2 to 52, 56 to 61))
The photosensitive coloring compositions (RB-2 to 52) are the same as the photosensitive coloring composition (RB-1) except that the types of the coloring composition, the blue composition, and the resin solution are changed as shown in Table 3. 55-60) was prepared. Here, the blending amounts (parts by mass) of the blue composition and the coloring composition are x = 0.150 and y = 0.060 with a C light source after firing at 230 ° C. when the coated substrate is prepared. The ratio was selected to match the chromaticity. The total of the blue composition and the coloring 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 (BASF's "Irgacure 907"))
Photopolymerization Initiator: 0.5 parts (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime) ( BASF "Irgacure OXE02")
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 / PB 15: 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 (BASF's "Irgacure 907"))
Photopolymerization Initiator: 0.5 parts (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime) ( BASF "Irgacure OXE02")
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-carbazole-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 filters>
The lightness (spectral transmittance) and contrast ratio (CR) of the obtained photosensitive coloring composition were evaluated by the following methods. The results are shown in Table 3.
However, Examples 3-1 and 3-2 are reference examples.

(Brightness (spectral transmittance))
The photosensitive coloring composition was applied to a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm with a spin coater ^{, exposed to ultraviolet rays at an exposure amount of 50 mJ / cm 2} , and then 0.2% by mass of carbon dioxide at 23 ° C. It was spray-developed with an aqueous sodium solution for 30 seconds and baked in an oven at 230 ° C. for 30 minutes to obtain a coated substrate of the obtained photosensitive coloring composition. The brightness (spectral transmittance) was measured using the obtained coated substrate. The blue coating film made of the photosensitive coloring composition was fired at 230 ° C. and then applied with a C light source so as to match the chromaticity of x = 0.150 and y = 0.060. The brightness (spectral transmittance) in the XYZ colorimetric chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). The judgment criteria are as follows. In the evaluation results, ○ is a good result, and △ corresponds to a level where there are some problems but no problems in use.
◯: 11.8 or more Δ: 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 the brightness measurement. The judgment criteria are as follows. In the evaluation results, ○ is a good result, and △ corresponds to a level where there are some problems but no problems in use.
◯: 11000 or more Δ: 8000 or more and 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 brightness but also in contrast ratio, which is the effect of suppressing the fluorescence of the xanthene dye (A2). Is considered to be.

<Manufacturing of color filters>
(Manufacture 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) Ellis Ritol Hexaacrylate)
Photopolymerization initiator: 1.0 part (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (BASF's "Irgacure 907"))
Photopolymerization Initiator: 0.5 parts (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime) ( BASF "Irgacure OXE02")
Organic solvent: 39.0 parts (ethylene glycol monomethyl ether acetate)

(Manufacture 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) Ellis Ritol Hexaacrylate)
Photopolymerization initiator: 1.0 part (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (BASF's "Irgacure 907"))
Photopolymerization Initiator: 0.5 parts (ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl], 1- (O-acetyloxime) ( BASF "Irgacure OXE02")
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 onto the substrate with a spin coater to form a colored film. The coating film was irradiated with ultraviolet rays of ^{150 mJ / cm 2} using an ultra-high pressure mercury lamp via a photomask. Next, the unexposed portion was removed by spray development with an alkaline developer consisting of a 0.2 mass% sodium carbonate aqueous solution, washed with ion-exchanged water, and the substrate was heated at 220 ° C. for 20 minutes to obtain a red filter segment. Was formed. Here, the red filter segment was adjusted to match the chromaticity of x = 0.645 and y = 0.323 in the C light source after the heat treatment at 220 ° C. (hereinafter, also used for green and blue). Further, by the same method, the green filter segment is adjusted to match the chromaticity of x = 0.290 and y = 0.600 using the green photosensitive coloring composition (RG-1), and the blue filter segment is set to match the chromaticity of x = 0.290 and y = 0.600. The photosensitive coloring composition (RB-4) of the present invention is used to match the chromaticity of x = 0.150 and y = 0.060, and each filter segment is formed to form a color filter (CF-1). Got

[Examples 4-1 to 7 and Comparative Examples 4-1 and 2]
(Color filter (CF-2-9))
Hereinafter, color filters (CF-2 to 9) were obtained in the same manner as the color filter (CF-1) except that the combination of the red photosensitive coloring composition and the blue photosensitive coloring composition shown in Table 4 was changed. ..

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

(Brightness (spectral transmittance))
The brightness (spectral transmittance) in the XYZ colorimetric chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). The judgment criteria are as follows. In the evaluation results, ○ is a good result, and △ corresponds to a level where there are some problems but no problems in use.
◯: 28.80 or more Δ: 28.60 or more and less than 28.80 ×: less than 28.60

(Contrast ratio)
The judgment criteria are as follows. In the evaluation results, ○ is a good result, and △ corresponds to a level where there are some problems but no problems in use.
◯: 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 coloring composition for a color filter containing the colorant for a color filter of the present invention has high brightness and contrast.

Claims (8)

A coloring composition for a color filter 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 (3) and a xanthene dye (A2) having fluorescence.

General formula (3)

[In general formula (3),
R ₃ and R ₄ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent.
Y ₂ may have 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, or 6 carbon atoms which may have a substituent. Represents 10 to 10 aryl groups.
R ₄ and Y ₂ may be combined to form a ring containing a nitrogen atom.
T ₅ and T ₆ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or 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 resin Z + having a cationic group in the side chain.} ] Xanthene dyes (A1 ') content of the general formula (3) xanthene dye represented by (A1' 0.1 wt% to 10.0 wt of the total of) and xanthene dyes having fluorescence (A2) %. The coloring composition for a color filter according to claim 1. The coloring composition for a color filter according to claim 1 or 2 , wherein the xanthene dye (A1') represented by the general formula (3) is a salt-forming compound ^{with a resin Z +} having a cationic group in the side chain. The coloring composition for a color filter according to any one of claims 1 to 3, wherein the fluorescent xanthene dye (A2) is a salt-forming compound of a xanthene acid 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 4 , wherein the coloring agent further contains an organic pigment. The coloring composition for a color filter according to any one of claims 1 to 5 , further comprising at least one of a photopolymerizable monomer and a photopolymerization initiator. A color filter formed by the coloring composition for a color filter according to any one of claims 1 to 6. 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 an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent.
T ₅ and T ₆ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent.
Y ₂ may have 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, or 6 carbon atoms which may have a substituent. Represents 10 to 10 aryl groups.
R ₄ and Y ₂ may be combined to 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 resin Z + having a cationic group in the side chain.} ]