JP6958128B2 - Coloring compositions and color filters for color filters - Google Patents

Description

The present invention includes a color liquid crystal display device, a coloring composition for a color filter used for manufacturing a color filter used in a color image pickup element, an organic EL device, and the like, and a color having a filter segment formed by using the coloring composition. It's about filters.

When a dye is used as a colorant in a color filter coloring composition, it has a problem that its heat resistance is inferior to that of a pigment. So far, solutions have been studied as in Patent Document 1, but the current situation is that they do not satisfy sufficient resistance for color filters. In Patent Document 2, heat resistance is obtained by adding an ionic compound having a specific structure (a metal salt of a specific structure anion or an organic cation salt) to a salt-forming dye obtained by salt-forming a resin having a cation site in a side chain and an anionic dye. However, since the solubility of the ionic compound in the organic solvent is low, the stability of the coloring composition containing the dye with time is very poor, and it is difficult to put it into practical use.

Japanese Unexamined Patent Publication No. 2012-098522 Japanese Unexamined Patent Publication No. 2016-133604

An object of the present invention is to use a high-brightness coloring composition for a color filter, which can withstand a heat treatment at 230 ° C., has excellent heat resistance and solvent resistance, and has excellent storage stability over time, and the coloring composition for a color filter. It is to provide a high-brightness color filter formed by the above.

As a result of diligent studies to achieve the above object, the present inventor has formed a structural unit in which a cationic group having a specific structure and an anionic dye are salted in one molecule, and a cation having a specific structure. By containing a salt-forming compound containing a structural unit obtained by salting a sex group and an anion having a specific structure, a coloring composition for a high-brightness color filter having excellent solvent resistance and heat resistance and excellent storage stability over time. I found that I could get things.

［一般式（１）中、Ｒ^１は水素原子又は置換基を有してもよいアルキル基を表す。Ｒ^２〜Ｒ^４はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基又は置換基を有してもよいアリール基を表し、Ｒ^２〜Ｒ^４の内２つが互いに結合して環を形成しても良い。Ｑ^１はアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^５−又は−ＣＯＯ−Ｒ^５−を表し、Ｒ^５はアルキレン基を表す。Ｙ⁻はアニオン性色素を表す。］
一般式（２）

［一般式（２）中、Ｒ^６は水素原子又は置換基を有してもよいアルキル基を表す。Ｒ^７〜Ｒ^９はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基又は置換基を有してもよいアリール基を表し、Ｒ^７〜Ｒ^９の内２つが互いに結合して環を形成しても良い。Ｑ^２はアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^１０−又は−ＣＯＯ−Ｒ^１０−を表し、Ｒ^１０はアルキレン基を表す。
Ｚ⁻は、下記一般式（２ａ）で表わされるアニオン、下記一般式（２ｂ）で表わされるアニオン、下記一般式（２ｃ）で表わされるアニオン又は下記一般式（２ｄ）で表わされるアニオンを表す。］

〔一般式（２ａ）において、Ｒ^１１はハロゲン化炭化水素基を示し、Ｐはリン原子を示し、Ｈａｌはハロ基を示し、Ｒ^１１、Ｈａｌが各々複数存在する場合には、同一でも異なってもよい。ｃは１〜６の整数を示す。〕

〔一般式（２ｂ）において、Ｒ^１２はハロゲン化炭化水素基、シアノ基若しくはニトロ基で置換されたフェニル基又はシアノ基で置換されたフェニル基を示し、Ｂはホウ素原子を示し、Ｈａｌはハロ基を示し、Ｒ^１２、Ｈａｌが各々複数存在する場合には、同一でも異なってもよい。ｄは１〜４の整数を示す。〕

〔一般式（２ｃ）において、Ｒ^３１及びＲ^３２はそれぞれ独立に、スルホニル基で連結されていても良いハロゲン化炭化水素基、シアノ基又はＦＳＯ_２基を示し、Ｒ^３１及びＲ^３２が共にスルホニル基で連結されていても良いハロゲン化炭化水素基である場合、互いに結合して環を形成してもよい。ただし、Ｒ^３１及びＲ^３２の少なくとも一つはハロゲン化炭化水素基又はシアノ基である。〕

〔一般式（２ｄ）において、Ｒ^１４は、窒素原子又は酸素原子を有する連結基により連結されていても良いハロゲン化炭化水素基を示す。〕 That is, the present invention is a coloring composition for a color filter containing at least a colorant, a binder resin and an organic solvent, wherein the colorant is a structural unit represented by the following general formula (1) and the following general in one molecule. The present invention relates to a coloring composition for a color filter containing a salt-forming compound having a structural unit represented by the formula (2).
General formula (1)

[In the general formula (1), R ¹ represents an alkyl group which may have a hydrogen atom or a substituent. R ^{2 to} R ⁴ 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, and R ² two of to R ⁴ may be bonded to each other to form a ring. Q ¹ is an alkylene group, an arylene group, ^{-CONH-R 5} - or ^{-COO-R 5} - represents, ^{R 5} represents an alkylene group. Y ⁻ represents an anionic dye. ]
General formula (2)

[In the general formula (2), R ⁶ represents an alkyl group which may have a hydrogen atom or a substituent. R ^{7 to} R ⁹ 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, and R ⁷ Two of ~ R ⁹ may be combined with each other to form a ring. Q ² is an alkylene group, an arylene group, ^{-CONH-R 10} - or ^{-COO-R 10} - ^{represents, R 10} represents an alkylene group.
Z ⁻ represents an anion represented by the following general formula (2a), an anion represented by the following general formula (2b), an anion represented by the following general formula (2c), or an anion represented by the following general formula (2d). ]

[In the general formula (2a), R ¹¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and ^{when a plurality of R 11} and H are present, they are the same but different. May be good. c represents an integer of 1 to 6. ]

[In the general formula (2b), R ¹² represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a phenyl group substituted with a cyano group, B represents a boron atom, and Hal represents a halo. It represents a group, when R ^{12, Hal} there are a plurality each of which may be the same or different. d represents an integer of 1 to 4. ]

[In the general formula (2c), R ³¹ and R ³² each independently represent a halogenated hydrocarbon group, a cyano group or _two ^{FSO groups which may be linked by a sulfonyl group, and both R 31} and R ³² are sulfonyl groups. In the case of halogenated hydrocarbon groups which may be linked by a group, they may be bonded to each other to form a ring. However, ^{at least one of R 31} and R ³² is a halogenated hydrocarbon group or a cyano group. ]

[In the general formula (2d), R ¹⁴ represents a halogenated hydrocarbon group that may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

Further, in the present invention, the salt-forming compound further comprises at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetane group, a t-butyl group, an isocyanate group and a (meth) acryloyl group. The present coloring composition for a color filter which has a structural unit which has.

The present invention also relates to the coloring composition for a color filter, wherein the salt-forming compound has a structural unit having an oxetane group and a structural unit having a t-butyl group.

Further, the present invention relates to the above-mentioned color in which the molar ratio of the structural unit represented by the general formula (1) to the structural unit represented by the following general formula (2) is 2/1 to 1/2 in the salt-forming compound. Regarding coloring compositions for filters.

^{Further, in the present invention, Z −} in the general formula (2) of the salt-forming compound is an anion represented by the following formula (2b-1), an anion represented by the following formula (2c-1), and the following formula (2c). The color composition for a color filter, which is at least one anion selected from the group consisting of the anions represented by -2).

The present invention also relates to the coloring composition for a color filter, wherein the binder resin contains an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain.

Further, in the present invention, the active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is an unsaturated ethylenic monomer having a carboxyl group and a single amount of another unsaturated ethylenic monomer. The present coloring composition for a color filter, which is a resin obtained by adding an unsaturated ethylenic monomer having an epoxy group to a part of side chain carboxyl groups of a copolymer with a body.

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 also relates to the above-mentioned coloring composition for a color filter, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

Further, the present invention relates to a color filter including a filter segment formed from the coloring composition for a color filter on a base material.

In the present invention, a structural unit obtained by salting a cationic group having a specific structure and an anionic dye and a structural unit obtained by salting a cationic group having a specific structure and an anion having a specific structure are used in one molecule. By containing the salt-forming compound, a coloring composition for a high-brightness color filter having excellent solvent resistance and heat resistance and excellent storage stability over time can be obtained.

Hereinafter, the present invention will be described in detail.
The coloring composition for a color filter of the present invention is a coloring composition for a color filter containing at least a coloring agent, a binder resin and an organic solvent, and the coloring agent is represented in one molecule by the following general formula (1). It is characterized by containing a salt-forming compound having a structural unit and a structural unit represented by the following general formula (2).

<Colorant>
<Salt-forming compound>
The coloring composition of the present invention contains, as a colorant, a salt-forming compound having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) in one molecule.

［一般式（１）中、Ｒ^１は水素原子又は置換基を有してもよいアルキル基を表す。Ｒ^２〜Ｒ^４はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基又は置換基を有してもよいアリール基を表し、Ｒ^２〜Ｒ^４の内２つが互いに結合して環を形成しても良い。Ｑ^１はアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^５−又は−ＣＯＯ−Ｒ^５−を表し、Ｒ^５はアルキレン基を表す。Ｙ⁻はアニオン性色素を表す。］ [Structural unit represented by the general formula (1) and the structural unit represented by the following general formula (2)]
General formula (1)

[In the general formula (1), R ¹ represents an alkyl group which may have a hydrogen atom or a substituent. R ^{2 to} R ⁴ 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, and R ² two of to R ⁴ may be bonded to each other to form a ring. Q ¹ is an alkylene group, an arylene group, ^{-CONH-R 5} - or ^{-COO-R 5} - represents, ^{R 5} represents an alkylene group. Y ⁻ represents an anionic dye. ]

［一般式（２）中、Ｒ^６は水素原子又は置換基を有してもよいアルキル基を表す。Ｒ^７〜Ｒ^９はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基又は置換基を有してもよいアリール基を表し、Ｒ^７〜Ｒ^９の内２つが互いに結合して環を形成しても良い。Ｑ^２はアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^１０−又は−ＣＯＯ−Ｒ^１０−を表し、Ｒ^１０はアルキレン基を表す。
Ｚ⁻は、下記一般式（２ａ）で表わされるアニオン、下記一般式（２ｂ）で表わされるアニオン、下記一般式（２ｃ）で表わされるアニオン又は下記一般式（２ｄ）で表わされるアニオンを表す。］ General formula (2)

[In the general formula (2), R ⁶ represents an alkyl group which may have a hydrogen atom or a substituent. R ^{7 to} R ⁹ 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, and R ⁷ Two of ~ R ⁹ may be combined with each other to form a ring. Q ² is an alkylene group, an arylene group, ^{-CONH-R 10} - or ^{-COO-R 10} - ^{represents, R 10} represents an alkylene group.
Z ⁻ represents an anion represented by the following general formula (2a), an anion represented by the following general formula (2b), an anion represented by the following general formula (2c), or an anion represented by the following general formula (2d). ]

〔一般式（２ａ）において、Ｒ^１１はハロゲン化炭化水素基を示し、Ｐはリン原子を示し、Ｈａｌはハロ基を示し、Ｒ^１１、Ｈａｌが各々複数存在する場合には、同一でも異なってもよい。ｃは１〜６の整数を示す。〕

[In the general formula (2a), R ¹¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and ^{when a plurality of R 11} and H are present, they are the same but different. May be good. c represents an integer of 1 to 6. ]

〔一般式（２ｂ）において、Ｒ^１２はハロゲン化炭化水素基、シアノ基、ニトロ基で置換されたフェニル基又はシアノ基で置換されたフェニル基を示し、Ｂはホウ素原子を示し、Ｈａｌはハロ基を示し、Ｒ^１２、Ｈａｌが各々複数存在する場合には、同一でも異なってもよい。ｄは１〜４の整数を示す。〕

[In the general formula (2b), R ¹² represents a halogenated hydrocarbon group, a cyano group, a phenyl group substituted with a nitro group or a phenyl group substituted with a cyano group, B represents a boron atom, and Hal represents a halo. It represents a group, when R ^{12, Hal} there are a plurality each of which may be the same or different. d represents an integer of 1 to 4. ]

〔一般式（２ｃ）において、Ｒ^３１及びＲ^３２はそれぞれ独立に、スルホニル基で連結されていても良いハロゲン化炭化水素基、シアノ基又はＦＳＯ_２基を示し、Ｒ^３１及びＲ^３２が共にスルホニル基で連結されていても良いハロゲン化炭化水素基である場合、互いに結合して環を形成してもよい。ただし、Ｒ^３１及びＲ^３２の少なくとも一つはハロゲン化炭化水素基又はシアノ基である。〕

[In the general formula (2c), R ³¹ and R ³² each independently represent a halogenated hydrocarbon group, a cyano group or _two ^{FSO groups which may be linked by a sulfonyl group, and both R 31} and R ³² are sulfonyl groups. In the case of halogenated hydrocarbon groups which may be linked by a group, they may be bonded to each other to form a ring. However, ^{at least one of R 31} and R ³² is a halogenated hydrocarbon group or a cyano group. ]

〔一般式（２ｄ）において、Ｒ^１４は、窒素原子又は酸素原子を有する連結基により連結されていても良いハロゲン化炭化水素基を示す。〕

[In the general formula (2d), R ¹⁴ represents a halogenated hydrocarbon group that may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

^{Examples of the alkyl group in R 1} of the general formula (1) include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group and a cyclohexyl group. .. As 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 1} has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group. Among these, as R ^1, a hydrogen atom or a methyl group is most preferable.

^{Examples of the alkyl group in R 2 to} R ⁴ of the general formula (1) include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-. Dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1, 3,3-Tetramethylbutyl, 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.

The alkenyl group for ^R 2 to R ⁴ in the general formula (1), for example, straight-chain or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl , 1-Methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl and 3-cyclohexenyl, etc.) Etc.). 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 2 to} R ⁴ of the general formula (1) include a monocyclic aryl group (phenyl, etc.), a condensed polycyclic aryl group (naphthyl, anthraceny, phenanthrenyl, anthracinolyl, fluorenyl, naphthoquinolyl, etc.) and Aromatic heterocyclic hydrocarbon groups (thienyl (group derived from thiophene), frill (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9- Examples thereof include oxoxanthenyl (group derived from xanthone) and 9-oxothioxanthenyl (group derived from thioxanthone).

^{When the alkyl group, alkenyl group or aryl group in R 2 to} R ⁴ of the general formula (1) has a substituent, the substituent may be, for example, a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group or an acyl group. Examples thereof include a substituent selected from a group, 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 2 to} R ⁴ of the general formula (1), an unsubstituted alkyl group is particularly preferable from the viewpoint of stability. Further, ^{two of R 2 to} R ⁴ may be bonded to each other to form a ring.

The alkylene and arylene groups in to Q ¹ Formula (1) include one group obtained by removing a hydrogen atom of the alkyl group and the aryl group in R ¹ to R ⁴ above.

Examples of the alkylene group in ^{R 5} of the general formula (1) include a group obtained by removing one hydrogen atom of the alkyl group in ^{R 1 to} R ^{4 described above.}

The to ^{Q 1} Formula (1), from the viewpoint of the polymerizable and ^{availability, -CONH-R 5 -, -} COO-R 5 - is preferably. Also, R ⁵ is a methylene group, an ethylene group, a propylene group, more preferably a butylene group, and particularly preferably an ethylene group.

^{The alkyl group in R 6} of the general formula (2) and the substituent which may be possessed are synonymous with the alkyl group and the substituent which may be possessed in ^{R 1} of the general formula (1) described above.

The alkyl group, alkenyl group, aryl group and optionally having substituent in ^{R 7 to} R ⁹ of the general formula (2) include the ^{alkyl group in R 2 to} R ⁴ of the general formula (1) described above. Is synonymous with a good substituent.

Alkylene group and arylene group in Q ² in the general formula (2) has the same definition as the alkylene and arylene groups in to Q ¹ the above general formula (1).

^{The alkylene group in R 10} of the general formula (2) is synonymous with the alkylene group in ^{R 5} of the general formula (1) described above.

[Y ⁻ : Anionic dye]
^{As the anionic dye in Y −} of the general formula (1), known ones can be adopted without limitation, and specifically, a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, or these in the molecule. Examples thereof include anions derived from anionic dyes having a metal salt of.

(Anionic dye)
Examples of anionic dyes include anthraquinone-based anionic dyes, monoazo-based anionic dyes, disazo-based anionic dyes, oxazine-based anionic dyes, aminoketone-based anionic dyes, xanthene-based anionic dyes, and quinoline-based anionic dyes. Examples thereof include triphenylmethane-based anionic dyes. Specific examples of anionic dyes are shown below by color index numbers.

Examples of red dyes include C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like can be mentioned.

In addition, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171 and 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like can also be used.

Examples of yellow dyes include C.I. I. Acid Yellow 2,3,4,5,6,7,8,9,9: 1,10,11,11: 1,12,13,14,15,16,17,17:1,18,20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191 and 192, 199 and the like can be mentioned.

In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like can also be used.

Examples of orange dyes include C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1, 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like can be mentioned.

In addition, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114 and the like can also be used.

As a blue dye, C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261 and 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

In addition, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263 and the like can also be used.

As a purple dye, C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. Can be mentioned.

In addition, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like can also be used.

As a green dye, C.I. I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, Examples thereof include 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94 and 95.
In addition, C.I. I. Direct greens 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80 and the like can also be used.

[一般式（４）中、Ｘ_１及びＸ_３は、それぞれ独立して、置換基を有していてもよい炭素数１〜２０のアルキル基を表す。Ｘ_２及びＸ_４は、それぞれ独立して、置換基を有していてもよいアリール基を表し、少なくともいずれか一方がスルホ基を有するアリール基である。] In addition, a red dye represented by the general formula (4) can also be used.
General formula (4)

[In the general formula (4), X ₁ and X ₃ each independently represent an alkyl group having 1 to 20 carbon atoms which may have a substituent. X ₂ and X ₄ each independently represent an aryl group which may have a substituent, and at least one of them is an aryl group having a sulfo group. ]

_{The alkyl groups in X 1} and X ₃ of the general formula (4) are synonymous with the alkyl groups in ^{R 1 to} R ⁴ of the general formula (1) described above.
_{The aryl group in X 2} and X ₄ of the general formula (4) is synonymous with the aryl group in ^{R 2 to} R ⁴ of the general formula (1) described above.
The substituents that may be possessed _{in X 1 to X 4} of the general formula (4) are synonymous with the substituents that may be possessed ^{in R 1 to R 4} of the general formula (1) described above. However, at least one of the aryl groups in _{X 2} and X _{4 is substituted with a sulfo group.}

As the anionic dye, a red dye is preferable, and acid red 52, acid red 289, and a dye represented by the general formula (4) are particularly preferable.

[Z ⁻ : Anion having a specific structure]
In Z ⁻ of the general formula (2), the anion represented by the following general formula (2a), the anion represented by the following general formula (2b), the anion represented by the following general formula (2c), or the following general formula (2d). The represented anion will be described.

〔一般式（２ａ）において、Ｒ^１１はハロゲン化炭化水素基を示し、Ｐはリン原子を示し、Ｈａｌはハロ基を示し、Ｒ^１１、Ｈａｌが各々複数存在する場合には、同一でも異なってもよい。ｃは１〜６の整数を示す。〕 (Anion represented by the general formula (2a))

[In the general formula (2a), R ¹¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and ^{when a plurality of R 11} and H are present, they are the same but different. May be good. c represents an integer of 1 to 6. ]

Examples of the Hall of the general formula (2a) include a fluoro group, a chloro group, a bromo group, and an iodine group, and a fluoro group is preferable.

^{The halogenated hydrocarbon group in R 11} of the general formula (2a) is preferably an alkyl group substituted with a halogen atom or an aryl group substituted with a halogen atom, and more preferably an alkyl fluoride group or an aryl fluoride. Is the basis. A aryl fluoride group is more preferable, and a pentafluorophenyl group is particularly preferable.

Typical examples of the anion represented by the general formula (2a) are (CF ₃ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [( _{CF 3) 2 CF] 2 PF} 4 -, [(CF 3) 2 CF] 3 PF 3, (n-C 3 F 7) 2 PF 4 -, (n-C 3 F 7) 3 PF 3 -, ( _{n-C 4 F 9) 3} PF 3 -, (C 2 F 5) (CF 3) 2 PF 3 -, [(CF 3) 2 CFCF 2] 2 PF 4 -, [(CF 3) 2 CFCF 2] _{3 PF 3, (n-C} 4 F 9) 2 PF 4 -, (n-C 4 F 9) 3 PF 3 -, (C 2 F 4 H) (CF 3) 2 PF 3 -, (C 2 F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ^{− and the} like can be mentioned. Among ^{_{them, PF 6 -, (C 2}} F 5) 2 PF 4 -, (C 2 F 5) 3 PF 3 -, (n-CF 7) 3 PF 3 -, (n-C 4 F 9) 3 PF 3 ^{_{-, [(CF 3) 2}} CF] 3 PF 3 -, [(CF 3) 2 CF] 2 PF 4 -, [(CF 3) 2 CFCF 2] 3 PF 3 -, [(CF 3) 2 CFCF 2 ] ₂ PF ₄ ^- is preferable.

〔一般式（２ｂ）において、Ｒ^１２はハロゲン化炭化水素基、シアノ基若しくはニトロ基で置換されたフェニル基又はシアノ基で置換されたフェニル基を示し、Ｂはホウ素原子を示し、Ｈａｌはハロ基を示し、Ｒ^１２、Ｈａｌが各々複数存在する場合には、同一でも異なってもよい。ｄは１〜４の整数を示す。〕 (Anion represented by the general formula (2b))

[In the general formula (2b), R ¹² represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a phenyl group substituted with a cyano group, B represents a boron atom, and Hal represents a halo. It represents a group, when R ^{12, Hal} there are a plurality each of which may be the same or different. d represents an integer of 1 to 4. ]

Hal in the general formula (2b) is synonymous with Hal in the general formula (2a) described above.

R ² represents a halogenated hydrocarbon group, a cyano group, or a nitro group or a phenyl group substituted with a cyano group, and the halogenated hydrocarbon group is a halogenated hydrocarbon as ^{Z − in the above general formula (1).} The halogenated hydrocarbon group mentioned in the description of the anion having a hydrogen group can be mentioned. In the present invention, R ² is preferably a halogenated hydrocarbon group, preferably an alkyl fluoride group, or preferably an aryl fluoride group.

^{The halogenated hydrocarbon group in R 12} of the general formula (2b) is synonymous with the halogenated hydrocarbon group in ^{R 11} of the general formula (2a) described above. R ¹² is preferably a halogenated hydrocarbon group, preferably an alkyl fluoride group or an aryl fluoride group.

Typical examples of the anion represented by the general formula (2b) are (CF ₃ ) ₄ B ⁻ , CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (CF 3). C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ^{_{2 BF -, (C 6 F}} 5) 4 B -, [(CF 3) 2 C 6 H 3] 4 B -, (CF 3 C 6 H 4) 4 B -, (C 6 F 5) 2 BF 2 ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B ( CN) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F ₅ ) ₃ B (CN) ⁻ , (C ₂ F ₅ ) ₂ B ^{_{(CN) 2 -, (n}} -C 3 F 7) 3 B (CN) -, (n-C 4 F 9) 3 B (CN) -, (n-C 4 F 9) 2 B (CN) 2 ^{_{-, (n-C 6 F}} 13) 3 B (CN) -, (CHF 2) 3 B (CN) -, (CHF 2) 2 B (CN) 2 -, (CH 2 CF 3) 3 B (CN ) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH) _{2 CH 2 C 3 F 7)} 2 B (CN) 2 -, (n-C 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B (CN) -, tetrakis (penta Fluorophenyl) borate anion and the like. Among ^{_{them, BF 4 -, B (CN}} ) 3 F -, (CF 3) 4 B -, (C 6 F 5) 4 B -, [(CF 3) 2 C 6 H 3] 4 B -, tetrakis (penta Fluorophenyl) borate anion is preferred.

〔一般式（２ｃ）において、Ｒ^３１及びＲ^３２はそれぞれ独立に、スルホニル基で連結されていても良いハロゲン化炭化水素基、シアノ基又はＦＳＯ_２基を示し、Ｒ^３１及びＲ^３２が共にスルホニル基で連結されていても良いハロゲン化炭化水素基である場合、互いに結合して環を形成してもよい。ただし、Ｒ^３１及びＲ^３２の少なくとも一つはハロゲン化炭化水素基又はシアノ基である。〕 (Anion represented by the general formula (2c))

[In the general formula (2c), R ³¹ and R ³² each independently represent a halogenated hydrocarbon group, a cyano group or _two ^{FSO groups which may be linked by a sulfonyl group, and both R 31} and R ³² are sulfonyl groups. In the case of halogenated hydrocarbon groups which may be linked by a group, they may be bonded to each other to form a ring. However, ^{at least one of R 31} and R ³² is a halogenated hydrocarbon group or a cyano group. ]

^{The halogenated hydrocarbon group in R 31} and R ³² of the general formula (2c) is synonymous with the halogenated hydrocarbon group in ^{R 11} of the general formula (2a) described above. Further, R ³¹ and R ³² may form an aliphatic saturated hydrocarbon-based cyclic structure. The sulfonyl group in the halogenated hydrocarbon group which may be linked with a sulfonyl group is a linking group of N ⁻ and R ³¹ or N ⁻ and R ³² . R ³¹ and R ³² are preferably halogenated hydrocarbon groups that are independently linked by a sulfonyl group, more preferably a fluorinated alkylsulfonyl group or a fluorinated arylsulfonyl group, and are particularly excellent in heat resistance. Become.

Typical examples of anions represented by the general formula (2c) are [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF). ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ ) N (CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂₎ ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ⁻ , [(FSO ₂ ) N {CF ₃ CF ₂ (CF) ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ⁻ , [(CF ₃ SO ₂ ) ₂ N] ⁻ , [(CF ₃ CF ₂ SO ₂ ) ₂ N] ^- , [(CF ₃ CF ₂ CF ₂ SO ₂ ) ₂ N] ^- , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₂ N] ^- , [{(CF ₃ ) ₂ CFCF ₂ SO ₂ } ₂ N] ⁻ , [{CF ₃ CF ₂ (CF ₃ ) CFSO ₂ } ₂ N] ⁻ , [{(CF ₃ ) ₃ CSO ₂ } ₂ N] ⁻ , or the following compounds can be mentioned.

〔一般式（２ｄ）において、Ｒ^１４は、窒素原子又は酸素原子を有する連結基により連結されていても良いハロゲン化炭化水素基を示す。〕 (Anion represented by the general formula (2d))

[In the general formula (2d), R ¹⁴ represents a halogenated hydrocarbon group that may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

^{The halogenated hydrocarbon group in R 14} of the general formula (2d) is synonymous with the halogenated hydrocarbon group in ^{R 11} of the general formula (2a) described above. Halogenated hydrocarbon groups may be linked by -O-, -CO-, -COO-, -CO-NH- or the like. R ¹⁴ is preferably a halogenated hydrocarbon group, more preferably a fluorinated alkylsulfonyl group or a fluorinated arylsulfonyl group, and is particularly excellent in heat resistance.

As a typical example of the anion represented by the general formula (2d), for example, the anion represented by the following can be mentioned.

^{The Z −} of the general formula (2) is preferably an anion represented by the general formula (2b) or (2c), and particularly preferably an anion represented by the following formula.

[Manufacturing of salt-forming compounds]
The salt-forming compound of the present invention only needs to have a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2) in one molecule, and particularly preferably, the following. A vinyl resin having a cationic group in the side chain containing a structural unit represented by the general formula (3), an anionic dye, and an anionic metal salt represented by the above general formulas (2a) to (2d) or It is a salt-forming compound of an organic cation salt.

［一般式（３）中、Ｒ^２１は水素原子又は置換基を有してもよいアルキル基を表す。Ｒ^２２〜Ｒ^２４はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基又は置換基を有してもよいアリール基を表し、Ｒ^２２〜Ｒ^２４の内２つが互いに結合して環を形成しても良い。Ｑ^３はアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ^２５−又は−ＣＯＯ−Ｒ^５−を表し、Ｒ^２５はアルキレン基を表す。Ｕ⁻は無機又は有機のアニオンを表す。］ (Vinyl resin having a cationic group in the side chain)
General formula (3)

[In the general formula (3), R ²¹ represents an alkyl group which may have a hydrogen atom or 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, and R ^22. Two of ~ R ²⁴ may be combined with each other to form a ring. Q ³ are an alkylene group, an arylene group, ^{-CONH-R 25} - or ^{-COO-R 5} - ^{represents, R 25} represents an alkylene group. U ⁻ represents an inorganic or organic anion. ]

^{The alkyl group in R 21} of the general formula (3) and the substituent which may be possessed are synonymous with the alkyl group and the substituent which may be possessed in ^{R 1} of the general formula (1) described above.

The alkyl group, alkenyl group, aryl group and optionally having substituent in ^{R 22 to} R ²⁴ of the general formula (3) include the ^{alkyl group in R 2 to} R ⁴ of the general formula (1) described above. Is synonymous with a good substituent.

Alkylene group and arylene group in Q ³ of the general formula (3) has the same meaning as the alkylene and arylene groups in to Q ¹ the above general formula (1).

^{The alkylene group in R 25} of the general formula (3) is synonymous with the alkylene group in ^{R 5} of the general formula (1) described above.

^{As the inorganic or organic anion in U −} of the general formula (3), known ones can be adopted without limitation, and specifically, hydroxide ions; halogens such as chloride ion, bromide ion and iodide ion. Ions; carboxylate ions such as formate ions and acetate ions; carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, Further, complex ions such as hexacyanoferrate (III) acid ion 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 counter 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.

(Manufacturing method of vinyl resin having a cationic group in the side chain)
In order to obtain a vinyl resin having a cationic group in the side chain containing the structural unit represented by the general formula (3), an ethylenically unsaturated monomer having a quaternary ammonium base and another single amount are copolymerized. A method of copolymerizing an ethylenically unsaturated monomer having an amino group with another single amount to obtain a vinyl resin having an amino group, and then reacting with an onium chloride agent to perform ammonium chloride. May be obtained by.

Specific examples of the ethylenically unsaturated monomer that can be used to obtain a vinyl resin containing the structural unit represented by the general formula (3) are shown below. In the present specification, when either or both of "acrylic, methacryl" is indicated, it may be described as "(meth) acrylic". Similarly, when indicating either or both of "acryloyl and methacryloyl", it may be described as "(meta) acryloyl".

Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyl trimethylammonium chloride, (meth) acryloyloxyethyl triethylammonium chloride, (meth) acryloyloxyethyl dimethylbenzylammonium chloride, and (meth). ) Alkyl (meth) acrylate-based quaternary ammonium salts such as acryloyloxyethyl methylmorpholinoammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Examples thereof include alkyl (meth) acryloylamide-based quaternary ammonium salts such as ammonium chloride, dimethyldiallylammonium methylsulfate, and trimethylvinylphenylammonium chloride.

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 A (meth) 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.

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 chloride reaction is about 90 ° C. or lower, particularly preferably about 30 ° C. or lower when the vinyl monomer is ammonium chloride, and the reaction time is about 1 to 4 hours.

Alternatively, an alkoxycarbonylalkyl halide can be used as the onium chloride agent.

(Other monomers)
Examples of other ethylenically unsaturated monomers include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and (meth) acrylamide. , Vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferred.

Specific examples of such a vinyl monomer include the following compounds.

Examples of (meth) acrylic acid esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n- (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2 (meth) acrylate -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecil (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene g (meth) acrylate Recall monoethyl ether, (meth) acrylate triethylene glycol monomethyl ether, (meth) acrylate triethylene glycol monoethyl ether, (meth) acrylate polyethylene glycol monomethyl ether, (meth) acrylate polyethylene glycol monoethyl ether, ( Β-Phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, ( Octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, etc. Is done.

Examples of crotonic acid esters include butyl crotonic acid, hexyl crotonic acid and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of itaconic acid diesters include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconic acid.

Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylic amide, N-isopropyl (meth) acrylamide, N- n-Butyl acrylic (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylic amide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) Acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, diacetoneacrylamide and the like can be mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples include styrene, hydroxystyrene protected by a group that can be deprotected by an acidic substance (for example, t-Boc), methyl vinyl benzoate, and α-methyl styrene.

The other monomer preferably contains a thermally crosslinkable functional group. In the heating step in the production of the color filter, the heat-crosslinkable functional groups contained in the resin contained in the coloring composition for the color filter form crosslinks to form a strong film and prevent the color change of the coating film. As a result, the heat resistance can be improved, and the solvent resistance is also improved.

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, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, and an epoxy. Examples thereof include a group, a mercapto group, an isocyanate group, an allyl group, and a (meth) acrylic group. 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. From the viewpoint of alkali developability, it is preferable to have a carboxyl group.

Specific examples of the monomer having a thermally crosslinkable functional group are shown below.
Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate. Examples thereof include 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and caprolactone adducts of these monomers (the number of addition moles is preferably 1 to 5).

Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like, and the ethylenically unsaturated monomer having a carboxylic acid anhydride group. Examples of the saturated monomer include maleic anhydride, itaconic anhydride and the like.

Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, and 3- (acryloyloxymethyl) 3-ethyl. Oxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and Examples thereof include 3- (methacryloyloxymethyl) 3-hexyloxetane.

Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

Examples of the ethylenically insatiable monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, and 4-isocyanate butyl acrylate.

The isocyanate group also includes a blocked isocyanate group and can be preferably used. The blocked isocyanate group can be deprotected by heating to regenerate an active isocyanate group while suppressing the reactivity of the isocyanate group by protecting the isocyanate group with another functional group under normal conditions. Indicates an isocyanate block body. Commercially available products of such an ethylenically unsaturated monomer having a blocked isocyanate group include, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Carens MOI-BP, manufactured by Showa Denko KK); 2-(0- [1'methylprovideneamino] carboxyamino) ethyl methacrylate (Karenzu MOI-BM, manufactured by Showa Denko) and the like can be mentioned.

To introduce a (meth) acryloyl group as a thermocrosslinkable functional group,
A method in which a vinyl resin having a cationic group in the side chain is obtained, and then the functional group of the vinyl resin is reacted with a functional group capable of reacting with the functional group and a compound having a (meth) acryloyl group. Can be mentioned. For example, by reacting a carboxyl group in a vinyl resin having a cationic group in the side chain having a carboxyl group with a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group, it can be used as a thermally crosslinkable functional group ( A vinyl resin having a meta) acryloyl group can be obtained. Further, by reacting the hydroxyl group of a vinyl resin having a cationic group in the side chain having a hydroxyl group with the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group, (meth) acryloyl is used as a thermally crosslinkable functional group. A vinyl-based resin having a group can be obtained.
At least one type of the heat-crosslinkable functional group needs to be contained in the vinyl resin, and two or more types may be contained.

Further, when two or more kinds of heat-crosslinkable functional groups are contained, the effect of cross-linking is improved when the heat-crosslinkable functional groups are a combination that is more easily reacted at the time of heating. For example, a combination of a hydroxyl group and a carboxyl group or a combination of an oxetanyl group and a carboxyl group not only obtains a strong coating film by thermal cross-linking, but also is alkaline due to the presence of the carboxyl group in the alkali development step before the thermal cross-linking. This is preferable because the developability is improved.
Further, a combination of a hydroxyl group and a blocked isocyanate group is also effective and preferable.
Further, the combination of the oxetanyl group and the t-butyl group is more preferable because the t-butyl group becomes a carboxyl group at the time of heating and reacts with the oxetanyl group. The oxetanyl group and the t-butyl group are more hydrophobic than the hydroxyl group and the carboxyl group, and even if they are contained more in the vinyl resin having a cationic group in the side chain, the compatibility with other resins is poor. Therefore, it is considered that a larger amount can be contained, and as a result, the crosslink density of the coating film can be increased and a stronger coating film can be obtained.

Examples of a method for obtaining a vinyl resin containing a structural unit represented by the general formula (3) suitable for the present invention include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. , Known methods can be used. Of these, free radical polymerization or living radical polymerization is preferable.

The vinyl-based resin containing the structural unit represented by the general formula (3) suitable for the present invention may be either a random resin or a block resin, but when the composition for a color filter of the present invention is a red composition, It is preferably a random resin.

The amount of ammonium base present in the vinyl resin containing the structural unit represented by the general formula (3) is not particularly limited, but the ammonium salt value of the resin is 10 to 200 mgKOH / g. It is preferably 20 to 130 mgKOH / g, more preferably 20 to 130 mgKOH / g.
Within this range, it is possible to achieve both coloring power and stability over time of foreign substances and the like.

In order for the ammonium salt value of the resin to satisfy the above range, an ethylenically unsaturated monomer having a quaternary ammonium base is preferably 4 to 74 with respect to the total amount of the ethylenically unsaturated monomers constituting the resin. It is mass%, more preferably 8 to 48 mass%.

The molecular weight of the vinyl resin containing the structural unit represented by the general formula (3) is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000 to 500. It is preferably 000, more preferably 3,000 to 15,000.

Further, the vinyl resin containing the structural unit represented by the general formula (3) preferably has a property of being soluble in a solvent widely used in a coloring composition for a color filter. As a result, a coating film that does not generate foreign matter can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

(Anionic dye)
The anionic dye salt-forming with the vinyl resin having a cationic group in the side chain containing the structural unit represented by the general formula (3) is described in the section of the anionic dye in ^{Y − of the general formula (1) described above.} It is synonymous with the anionic dye of.
As the anionic dye, a red dye is preferable, and acid red 52, acid red 289, and a dye represented by the general formula (4) are particularly preferable.

(Metal salt or organic cation salt of anion represented by general formulas (2a) to (2d))
General of anionic metal salts or organic cationic salts represented by the general formulas (2a) to (2d) for salt formation with a vinyl resin having a cationic group in the side chain containing the structural unit represented by the general formula (3). The anions represented by the formulas (2a) to (2d) are synonymous with the anions represented by the general formulas (2a) to (2d) in ^{Z −} of the above general formula (2).

The anionic metal salt or organic cation salt represented by the general formulas (2a) to (2d) is preferably an anion metal salt or organic cation salt represented by the general formula (2b) or the general formula (2c). Among them, as the anionic metal salt or organic cation salt represented by the general formula (2b), lithium tetrakis (pentafluorophenyl) borate is preferable, and the anion metal salt or the anion metal salt represented by the general formula (2c) is preferable. As the organic cation salt, lithium bis (trifluoromethanesulfonyl) imide and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfoneimide potassium are preferable.

(Salt formation)
The salt-forming compound of the present invention is an aqueous solution prepared by dissolving a resin having a cationic group in the side chain, an anionic dye, and an anionic metal salt or an organic cationic salt represented by the general formulas (2a) to (2d). Stirring or shaking is performed, or an aqueous solution of a resin having a cationic group in the side chain, an aqueous solution of an anionic dye, and an aqueous solution of an anionic metal salt or an organic cationic salt represented by the general formulas (2a) to (2d). Can be easily obtained by mixing with or under stirring or vibration. An aqueous solution of a resin having a cationic group in the side chain is stirred, and an aqueous solution of an anionic dye and an aqueous solution of an anionic metal salt or an organic cationic salt represented by the general formulas (2a) to (2d) are added dropwise thereto. The method of going is more preferable.
In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, since the salt composed of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. As the resin having a cationic group in the side chain and the anionic dye used, only one type may be used, or a plurality of types having different structures may be used.

The ratio of the resin having a cationic group in the side chain to the anionic dye and the metal salt or organic cationic salt of the anion represented by the general formulas (2a) to (2d) is the total cationic group of the resin and anionic. The salt-forming compound of the present invention can be suitably adjusted as long as the molar ratio of the dye and the anion represented by the general formulas (2a) to (2d) to the total anionic group is in the range of 10/1 to 1/1. A range of 2/1 to 1/1 is more preferable.

Further, if the ratio of the anionic dye to the metal salt or organic cation salt of the anion represented by the general formulas (2a) to (2d) is in the range of 5/1 to 1/5 in terms of molar ratio, it is the present invention. It is more preferable that the salt-forming compound can be preferably adjusted and is in the range of 2/1 to 1/2.
That is, the molar ratio of the structural unit represented by the general formula (1) to the structural unit represented by the following general formula (2) in the present invention is preferably 2/1 to 1/2. ..

[Pigment]
The coloring composition for a color filter of the present invention further contains a pigment as a coloring agent and can be used as a coloring composition for a color filter. As the pigment, an organic or inorganic pigment can be used alone or in combination of two or more. As the pigment, a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property is preferable, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the coloring composition for color filters are shown below by color index numbers.

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, It is represented by 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, or formula (5). Red pigments and the like can be mentioned. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 or a red pigment represented by the formula (5), more preferably C.I. I. Pigment Red 177, 209, 224, 242, 254, or a red pigment represented by the formula (5).

Equation (5)

Further, the red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 and other orange pigments and / or the yellow pigments described below may be used in combination.

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. Further, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment and the like described in JP-A-2004-333817, Patent No. 4893859 and the like can also be used.

Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58 can be mentioned. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Green 7, 36 or 58.
Further, the yellow pigment described later may be used in combination with the green coloring composition.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 192, Yellow pigments such as the quinophthalone pigments described in 193, 194, 196, 198, 199, 213, 214 and JP2012-226110A can be used. 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, 185 or the quinophthalone pigment described in JP-A-2012-226110, especially from the viewpoint of heat resistance, light resistance, and brightness of the filter segment. Therefore, as the yellow pigment, C.I. I. Pigment Yellow 138, 139, 150, and at least one selected from the quinophthalone pigments described in JP2012-226110A are preferable. More preferably, C.I. I. Pigment Yellow 83, 138, 139, 150, 185 or the quinophthalone pigment described in JP2012-226110A.

Examples of the quinophthalone-based pigment described in JP-A-2012-226110 include compounds represented by the following.

Cyan-colored compositions for forming cyan-colored filter segments include, for example, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and other blue pigments can be used alone or in combination.

Magenta coloring compositions for forming magenta filter segments include, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81 and red pigments can be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, and amber. , Synthetic iron black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

(Pigment miniaturization)
The pigment added to the coloring composition of the present invention is preferably finely divided by salt milling treatment or the like in order to correspond to high transmittance and high contrast. The primary particle size of the pigment is preferably 10 nm or more because it is well dispersed in the colorant carrier. Further, it is preferably 80 nm or less because a filter segment having high contrast can be formed. A particularly preferable range is the range of 20 to 60 nm.

When the pigment is salt-milled, 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% by mass based on the total weight of the pigment (100% by mass).

<Binder resin>
The binder resin is one that disperses a colorant or dyes and permeates a salt-forming compound, and examples thereof include a thermoplastic resin and a thermosetting resin.

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.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Further, since the coloring composition for a color filter of the present invention is in the form of an alkali-developing colored resist material, it is preferable to use an alkali-soluble vinyl-based resin copolymerized with an acidic group-containing ethylenically unsaturated monomer.

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, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (anhydrous) maleic acid 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, are preferably used because of their 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 resins having an unsaturated ethylenically double bond introduced by the methods (a) to (c) 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 monomers is used. , The carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added and reacted, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic 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 the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, 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 acid 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.

[Method (b)]
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 adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.
In this method, more hydroxyl groups derived from unsaturated ethylenic monomers having an epoxy group are generated as compared with the method (a). When the resin having a cationic group in the side chain used to obtain the salt-forming compound of the present invention contains an oxetanyl group and a t-butyl group as thermally crosslinkable functional groups, the method as a binder resin ( It is preferable to use the resin obtained in b) because it exhibits higher heat resistance.

[Method (c)]
As the method (c), 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 superpolymerizing 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 binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to 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.

When the binder resin is used as the photosensitive composition, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g from the viewpoint of dispersibility, permeability, developability and heat resistance of the pigment and the salt-forming compound. 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, fine patterns may not remain.

Since the binder resin has good film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 30% by mass or more based on the total weight of the colorant (100% by mass), and the colorant concentration is high and good. Since it can exhibit color characteristics, it is preferably used in an amount of 500% by mass 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-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-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 Hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.

Among them, since the pigments and salt-forming compounds of the present invention are well dispersed and dissolved, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like can be used. It is preferable to use aromatic alcohols such as glycol acetates and benzyl alcohols, and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and hygiene 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 mass.

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 mass by mass based on the total weight of the colorant (100% by mass). It is preferable to use it in an amount of%.

<Dispersion>
The coloring composition of the present invention comprises a colorant in a colorant carrier composed of a binder resin and a solvent, preferably together with a dispersion aid such as a dye derivative, in a three-roll mill, a two-roll mill, a sand mill, a kneader, or a kneader. It can be manufactured by finely dispersing it using various dispersion means such as an attritor. Further, the coloring composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other coloring agents and the like separately dispersed in a coloring agent carrier.

(Dispersion aid)
When the colorant is dispersed in the colorant carrier, 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. In the present description, the salt-forming compound (D) is also expected to play a role as a dispersant aid for pigments.

<< 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 phthalimide methyl 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 mass or more, more preferably 1% by mass or more, and most preferably 1% by mass or more, based on the total amount of the added pigment (100% by mass). It is 3% by mass or more. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40% by mass or less, more preferably 35% by mass or less, based on the total amount of the added pigment (100% by mass).

<< 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, polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphate esters, 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 Japan Lubrizol. 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.

Further, the resin-type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin-type dispersant having a carboxyl group.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride.
(S2) A weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. A resin-type dispersant that is a coalescence.

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Application Laid-Open No. 2008-029901, and Japanese Patent Application Laid-Open No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since the number of terminal hydroxyl groups is preferably plural, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example, a polymer having two hydroxyl groups at one end contains a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained therein. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and the carboxylic acid. Produces.

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and for example, a compound having a hydroxyl group. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. can get. Above all, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. The molecular weight and the like may differ slightly depending on various conditions, but theoretically the same can be obtained if the reaction conditions are the same as those of the raw material.

Each of the above resin-type dispersants has a main chain of a polyester moiety as a main chain and a vinyl polymer moiety as a side chain, and preferably the vinyl polymer moiety of the side chain has a thermally crosslinkable functional group. Have. Further, when the salt-forming compound of the present invention contains an oxetanyl group and / or a t-butyl group as a heat-crosslinkable functional group, the vinyl polymer moiety of the side chain of the resin type dispersant is an oxetanyl group and / or t-. It is preferable to contain a butyl group from the viewpoint of heat resistance.

Surfactants 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 alkylimidazoline, 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 mass, more preferably 0.1 to 45% by mass, based on the total amount of the added pigment (100% by mass). Is. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by mass, it is difficult to obtain the effect of addition, and when the blending amount is more than 55% by mass, 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 mass, and more preferably 10 to 300% by mass from the viewpoint of photocurability and developability, based on the total weight of the colorant (100% by mass). 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. Can be prepared in the form of. When the photopolymerization initiator is used, the blending amount is preferably 5 to 200% by mass, and 10 to 150% by mass from the viewpoint of photocurability and developability, based on the total amount of the colorant. 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; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole A system compound; an imidazole system compound; or a titanosen system compound or the like is 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 mass based on the total amount of the colorants in the coloring composition for a color filter (100% by mass), and are 10 from the viewpoint of photocurability and developability. More preferably, it is ~ 150% by mass.

<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, azulenium 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, methylphenylglycolate, 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, Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al., And " Examples thereof include, but are not limited to, the sensitizers described in "Special Functional Materials" (1986, CMC). 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 mass based on the total weight of the photopolymerization initiator contained in the coloring composition (100% by mass), and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50% by mass.

<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 mass based on the total weight of the coloring composition (100% by mass).

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 a glass plate despite having low surface tension lowering ability, and in an addition amount in which defects of the coating film due to foaming do not appear. 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 Esther and the like can be mentioned.

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.

<Epoxy compound>
An epoxy compound may be added to the coloring composition of the present invention, and a known compound having an epoxy group can be used without particular limitation.

Examples of the epoxy compound include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadienephenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, and biphenol type epoxy. Examples thereof include resins, bisphenol-A novolak type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

Specific examples of the phenol novolac type epoxy resin include Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC Corporation, and D.D. E. Examples thereof include N438, RE-306 manufactured by Nippon Kayaku Corporation, jER152 and jER154 manufactured by Mitsubishi Chemical Corporation.

Specific examples of the cresol novolac type epoxy resin include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, and Epicron N-665 manufactured by DIC Corporation. Examples thereof include EXP, Epicron N-672-EXP, EOCN-102S, EOCN-103S, EOCN-104S manufactured by Nippon Kayaku Co., Ltd., UVR-6650 manufactured by Union Carbide Co., Ltd., ESCN-195 manufactured by Sumitomo Chemical Industries, Ltd. and the like.

Specific examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H manufactured by Nippon Kayaku Corporation, TACTIX-742 manufactured by Dow Chemical Corporation, and jER E1032H60 manufactured by Mitsubishi Chemical Corporation. Can be mentioned.

Specific examples of the dicyclopentadienephenol type epoxy resin include Epicron EXA-7200 manufactured by DIC Corporation and TACTIX-556 manufactured by Dow Chemical Corporation.

Specific examples of the bisphenol type epoxy resin include jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Co., Ltd., and D.C. E. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., bisphenol-F type such as YDF-8170 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd. Epoxy resin and the like can be mentioned.

Specific examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Corporation, and bixylenol type epoxies such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation. Examples include resin.

Specific examples of the bisphenol A novolak type epoxy resin include Epicron N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

Specific examples of the naphthalene skeleton-containing epoxy resin include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., EXA-4750 manufactured by DIC Corporation, and the like.

Specific examples of the alicyclic epoxy resin include Seikiside 2021P, 2081, 2000 manufactured by Daicel Corporation, Epolide PB3600, PB4700, GT401, EHPE-3150, Cyclomer M100 and the like.

Specific examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

These epoxy compounds may be used alone or in admixture of two or more at any ratio as required.

The content of the epoxy compound used in the coloring composition of the present invention is (usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the solid content of the coloring composition. When the content is in the above range, the heat resistance is high and an excellent coating film can be obtained, which is preferable.

<Oxetane compound>
An oxetane compound may be added to the coloring composition of the present invention, and a known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or higher.

Examples of monofunctional oxetane groups include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-. 3- (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3-( Triethoxysilyl) propoxy] methyl} oxetane and the like.
Specific examples include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101 and 212 manufactured by Toagosei Co., Ltd., and the like.

Examples of bifunctional oxetane groups include 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-bis) Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene Glycose bis (3-ethyl-3-oxetanyl methyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanyl methyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3-Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethoxy) 3-Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) -modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) -modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3) -Oxetanyl methyl) ether and the like can be mentioned.
Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

If the oxetane group is bifunctional or higher,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kiss (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol Pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropantetrax (3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (for example, oxetane-modified phenol according to Patent No. 3783462). Examples thereof include a polymer obtained by radically polymerizing a (meth) acrylic monomer such as (Novolak resin or the like) or the above-mentioned OXE-30. Such a polymer can be obtained by using a known polymerization method.

The content of the oxetane compound used in the coloring composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on 100% by mass of the solid content of the coloring composition. When the content of the oxetane compound is in the above range, the heat resistance is high and an excellent coating film can be obtained, which is preferable.

<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. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, 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, dimethylamine). 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 mass with respect to the total amount of the thermosetting resin.

<UV absorber>
Further, the coloring composition of the present invention may contain an ultraviolet absorber, if necessary. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include a benzotriazole-based organic compound, a triazine-based organic compound, a benzophenone-based organic compound, a cyanoacrylate-based organic compound, and a salicylate-based organic compound. ..

The content of the ultraviolet absorber is preferably 5 to 70% by mass based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution cannot be ensured, and if it is more than the above, the sensitivity becomes low and the pixel peeling and the hole diameter are larger than the design value. There may be a problem such as becoming.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the solid content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be too high and the resolution may be deteriorated.

At this time, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

Examples of the benzotriazole-based organic compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-Hydroxy-5- (5-chloro-2H-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Phenyl-benzotriazole-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl- 5-Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1-dimethylethyl) -4- Hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-) Benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol.

More specifically, BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", " "TINUVIN 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, "RUNA-93" manufactured by Otsuka Chemical Co., Ltd., etc. Be done.

Examples of the triazine-based organic compound include 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like can be mentioned.

More specifically, "KEMISORB 102" manufactured by Chemipro Kasei Co., Ltd., "TINUVIN 400", "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", manufactured by BASF Corporation, Examples thereof include "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" manufactured by ADEKA, and "CYASORB UV-1164" manufactured by Sun Chemical.

Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid-3 water temperature, and 2-hydroxy-4-n-. Examples thereof include octoxybenzophenone and 2,2-di-hydroxy-4-methoxybenzophenone.

More specifically, "KEMISORB 10", "KEMISORB 11", "KEMISORB 11S", "KEMISORB 12", "KEMISORB 111" manufactured by Chemipro Kasei Co., Ltd., "SEESORB 101", "SEESORB 107", ADEKA manufactured by Cypro Kasei Co., Ltd. Examples thereof include "ADEKA STAB 1413" manufactured by the company.

<Thiol chain transfer agent>
The coloring composition of the present invention may contain a thiol-based chain transfer agent, if necessary. By using a thiol-based chain transfer agent together with a photopolymerization initiator, a chile radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation. High sensitivity.

Further, a polyfunctional aliphatic thiol bonded to an aliphatic group such as methylene or ethylene group having two or more SH groups is preferable. More preferably, it is a polyfunctional aliphatic thiol having 4 or more SH groups. By increasing the number of functional groups, the polymerization initiation function is improved, and the pattern can be cured from the surface to the vicinity of the substrate.

Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, Trimethylol Propanetristhioglycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetraxthiopropionate, Trimercaptopropionic Acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Triazine and the like can be mentioned, and preferred examples include ethylene glycol bisthiopropionate, trimethylpropantristhiopropionate, and pentaerythritol tetrakisthiopropionate.

These thiol-based chain transfer agents may be used alone or in admixture of two or more.

The content of the thiol chain transfer agent is preferably 1 to 10%, more preferably 2.0 to 8.0% of the total solid content of the photosensitive composition. In this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage rate, etc. are improved.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant can increase the transmittance of the coating film in order to prevent the composition contained in the coloring composition from being oxidized and yellowed by the thermal process at the time of thermosetting or ITO annealing. In particular, when the colorant concentration of the photosensitive coloring composition is high, the amount of the cross-linking component of the coating film is small, so that the yellowing of the thermal process is strong because the cross-linking component of high sensitivity is used and the amount of the photopolymerization initiator is increased. Phenomenon is seen.
Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical capture function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the ones preferable are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Agents can be mentioned.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Phenol) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
Specific examples include ADEKA's ADEKA STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320, Chemipro's KEMINOX101, 179, 76, 9425, BASF's IRGANOX1010, 1035, 1076, 1098, Examples thereof include 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, and Sianox CY-1790 and CY-2777 manufactured by Sun Chemical.

Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} Hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.
Specific examples include ADEKA's ADEKA STUB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA. -402F, LA-502XP, KAMISTAB29, 62, 77, 29, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin 249 manufactured by BASF, TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3329 manufactured by Sun Chemical Co., Ltd. UV-3853 and the like can be mentioned.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phosphite, Diphenyltridecylphosphite, Triphenylphosphite, Tris (nonylphenyl) phosphite, 4,4'isopropyridene diphenolalkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -Phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.
Specific examples include ADEKA's ADEKA TAB PEP-36, PEP-8, HP-10, ADEKA TAB 2112, 1178, 1500, C, 3013, TPP, BASF's IRGAFOS168, Clariant Chemicals' Hostanox P-EPQ, and the like. ..

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.
Specific examples include ADEKA ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemipro Kasei Co., Ltd.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.
Specific examples include ADEKA's ADEKA STAB LA-29, LA-31RG, LA-32, LA-36, -412S, Chemipro Kasei's KEMISORB71, 73, 74, 79, 279, and BASF's TINUVIN PS, 99-. 2, 384-2, 900, 928, 1130 and the like can be mentioned.

Examples of benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, and 2-hydroxy-4. -Octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4 Examples thereof include −methoxy-5 sulfobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.
Specific examples include ADEKA TAB 1413 manufactured by ADEKA, KEMISORB10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., UV-329, and the like.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Specific examples include ADEKA's ADEKA STAB LA-46 and F70, Chemipro Kasei's KEMISORB102, BASF's TINUVIN400, 405, 460, 477, 479, and Sun Chemical's Siresorb UV-1164.

Examples of the salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

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

The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the coloring composition because the spectral characteristics and sensitivity are good.

<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 phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-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 mass, preferably 0.05 to 5% by mass, based on the total amount of the colorant in the coloring composition (100% by mass).

<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, and more preferably 0.5 μm or more of coarse particles by means of centrifugation, sintering filter, membrane filter, or the like. 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 display after the paneling.

<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-developable or alkali-developable 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, ultraviolet exposure can be performed.

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, "parts" and "%" mean "parts by mass" and "% by mass".

(Average primary particle size of pigment)
For the average primary particle size of the pigment, use a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.) to measure the primary particle size of all pigment particles in the observation sample at 50,000 times, and calculate the average value. Using. When the particle shape was not spherical, the major axis and the minor axis were measured, and the value obtained by (major axis + minor axis) / 2 was taken as the particle diameter.

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

<Manufacturing of binder resin solution>
(Binder 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 26000. After cooling to room temperature, about 2 g of the resin solution is sampled, heated and dried 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 mass. It was added to prepare a binder resin solution 1. Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Binder 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 (Showa Denko's Karenz). 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 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 mass to prepare the binder resin solution 2. Prepared. The weight average molecular weight (Mw) was 18,000.

(Binder 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 from the dropping funnel over 2 hours, and the mixture was further stirred 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 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 mass to prepare the binder resin solution 3. Prepared. The weight average molecular weight (Mw) was 10,500.

(Binder 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) into 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 mass. Binder resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Manufacturing of finely divided pigments>
(Red refined pigment (P-1))
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 (“IRGAZINRED2030” manufactured by BASF Japan Ltd.), 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. This mixture is poured into 8000 parts of warm water, stirred with a high speed mixer for about 2 hours while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 85 ° C. for 24 hours. The mixture was dried to obtain 190 parts of a red finely divided pigment (P-1). The average primary particle size of the obtained pigment was 24.8 nm.

(Red refined pigment (P-2))
Red pigment C.I. I. 200 parts of Pigment Red 177, 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. This mixture is poured into 8000 parts of warm water, stirred with a high speed mixer for about 2 hours while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 85 ° C. for 24 hours. The mixture was dried to obtain 190 parts of a red finely divided pigment (P-2). The average primary particle size of the obtained pigment was 23.5 nm.

(Red refined pigment (P-3))
200 parts of the red pigment 1 of the formula (5), 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This mixture is poured into 8000 parts of warm water, stirred with a high speed mixer for 2 hours while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours. Then, 190 parts of a red finely divided pigment (P-3) was obtained. The average primary particle size of the obtained pigment was 29.3 nm.

Equation (5)

(Blue refined pigment (P-4))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyo Color's "Rionol Blue ES"), 800 parts of crushed salt, and 100 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 12 hours. bottom. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 98 parts of a blue fine pigment (P-4). The average primary particle size of the obtained pigment was 28.3 nm.

(Yellow refined pigment (P-5))
According to JP-A-2012-226110, a quinophthalone-based yellow pigment represented by the following formula (7) was synthesized.

Equation (7)

120 parts of the obtained quinophthalone-based yellow pigment represented by the formula (7), 1600 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 18 hours. bottom. This mixture is poured into 5000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. After drying, 118 parts of a quinophthalone-based yellow fine pigment (P-5) was obtained. The average primary particle size of the obtained pigment was 26.4 nm.

(Yellow refined pigment (P-6))
Yellow pigment C.I. I. 200 parts of Pigment Yellow 150, 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This mixture is put into 8000 parts of warm water, stirred with a high speed mixer for 2 hours while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours. Then, 190 parts of a yellow fine pigment (P-6) was obtained. The average primary particle size of the obtained pigment was 28.5 nm.

(Yellow refined pigment (P-7))
Yellow pigment C.I. I. 200 parts of Pigment Yellow 138, 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This mixture is poured into 8000 parts of warm water, stirred with a high speed mixer for 2 hours while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours. Then, 190 parts of a yellow fine pigment (P-7) was obtained. The average primary particle size of the obtained pigment was 27.1 nm.

(Yellow refined pigment (P-8))
Yellow pigment C.I. I. 200 parts of Pigment Yellow 139, 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This mixture is poured into 8000 parts of warm water, stirred with a high speed mixer for 2 hours while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours. Then, 190 parts of a yellow fine pigment (P-8) was obtained. The average primary particle size of the obtained pigment was 25.4 nm.

<Manufacturing of resin having a cationic group in the side chain>
(Resin B-1 solution having a cationic group in the side chain)
80.0 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, 25.0 parts of methyl methacrylate, 25.0 parts of n-butyl methacrylate, 30.0 parts of 2-ethylhexyl methacrylate, 20.0 parts of methacryloylaminopropyltrimethylammonium chloride, 47.0 parts of isopropyl alcohol, 2,2'-. After making 5.0 parts of azobis (2,4-dimethylvaleronitrile) and 18.0 parts of methyl ethyl ketone uniform, the mixture was charged in a dropping funnel, attached to a four-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 9000, and the mixture was cooled to 50 ° C. Then, isopropyl alcohol was added for adjustment to obtain a resin (B-1) having a cationic group in the side chain having a non-volatile content of 40% by mass. The ammonium salt value of the obtained resin was 54 mgKOH / g.

(Resin B-2 to B-4 solutions having a cationic group in the side chain)
Random resin (B-2 to B-3) solutions were obtained in the same manner as in B-1, except that the type and blending amount of the monomers were changed as shown in Table 1.

(Resin B-5 solution having a cationic group in the side chain)
25.0 parts of (3-ethyloxetane-3-yl) methyl acrylate, 40.0 parts of t-butyl acrylate, 5.0 parts of methacrylic acid in a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer. 10.0 parts of methyl methacrylate, 20.0 parts of dimethylaminoethyl methyl chloride salt methacrylate, and 1.6 parts of tetramethylethylenediamine 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. bottom. 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 15.0 parts of dimethylaminoethyl methyl chloride salt methacrylate as a second block monomer were added to this reactor, and the mixture was stirred while maintaining a nitrogen atmosphere at 100 ° C. , 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 Mw9200 and Mw / Mn = 1.5, and the reaction conversion rate was 98.5%. In this way, a block resin (B-5) having a quaternary ammonium salt value of 54 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 mass to block resin (block resin ( B-5) A solution was obtained.

(Resin B-6 solution having a cationic group in the side chain)
80.0 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, 35.0 parts of methyl methacrylate, 20.0 parts of butyl methacrylate, 5.0 parts of methacrylic acid, 20.0 parts of 2-hydroxyethyl methacrylate, 20.0 parts of methacryloylaminopropyltrimethylammonium chloride, 47.0 parts of isopropyl alcohol. , 2,2'-Azobis (2,4-dimethylvaleronitrile) (5.0 parts) and methylethylketone (18.0 parts) were homogenized, then charged into a dropping funnel, attached to a 4-port 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 9000, and the mixture was cooled to 50 ° C.
Then, 100.0 parts of N-methylpyrrolidone was added, the solvent was volatilized at 80 ° C., stripping was continued while further raising the temperature, and the temperature was raised to 95 ° C. At that time, the solvent was no longer volatilized. Then, 23.8 parts of 2-methacryloyloxyethyl isocyanate (Kalens MOI manufactured by Showa Denko) was added, 0.024 g of methylhydroquinone was added, and the mixture was reacted at 80 ° C. for 4 hours in an oxygen atmosphere. Isopropyl alcohol was added for adjustment to obtain a resin (B-6) having a cationic group in the side chain having a non-volatile content of 40% by mass. The ammonium salt value of the obtained resin was 41 mgKOH / g.

DMCMA: Dimethylaminoethyl methyl methacrylate tBMA: t-butyl methacrylate tBA: t-butyl acrylate MAA: MMA methacrylate: Methyl methacrylate HEMA: 2-hydroxymethacrylate 2EHMA: 2-ethylhexyl methacrylate BMA: butyl methacrylate MOI-BM: 2-(0- [1'-Methylpropylideneamino] carboxyamino) ethyl methacrylate (Karensu MOI-BM manufactured by Showa Denko)

<Manufacturing of anionic dye (C)>
(Anionic dye 1)
C. I. 45.0 parts of Acid Red, 45.3 parts of 1-iodopropane and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone, and the mixture was stirred at 90 ° C. for 6 hours. The obtained reaction solution was cooled to room temperature, added to 3000 parts of ethyl acetate, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were separated by filtration, washed with 2500 parts of ethyl acetate, and dried under reduced pressure at 60 ° C. overnight to obtain 47.6 parts of anionic dye.
The anion dye 1 has a structure in which the substituents _{of X 1 to} X _{4 in} the dye represented by the general formula (4) are shown in Table 2.

General formula (4)

<Manufacturing of salt-forming compounds>
(Salt-forming compound (D-1))
A resin solution (B-1) having a cationic group on the side chain of 50 parts was added to 2000 parts of water, and the mixture was sufficiently stirred and mixed. On the other hand, in 90 parts of water, 5.60 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared, and the solution was added dropwise to the resin solution. After the dropping, an aqueous solution prepared by dissolving 2.77 parts of lithium bis (trifluoromethanesulfonyl) imide in 90 parts of water was prepared, and the mixture was further added dropwise little by little. After the dropping, the mixture is stirred for 120 minutes and the reaction is sufficiently carried out. To confirm 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 using the point where the bleeding disappeared as the end point. Then, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 21 parts of C.I. I. A salt-forming compound (D-1) of acid red 52 and a resin (B-1) having a cationic group in the side chain was obtained.

(Salt-forming compounds D-2 to 21)
Hereinafter, salt-forming compounds D-2 to 21 were prepared in the same manner as D-1 except that the resins and dyes having a cationic group in the side chain were changed to those shown in Table 3.

Lithium bis (trifluoromethanesulfonyl) imide

1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide potassium

Tetrakis (pentafluorophenyl) lithium borate

Potassium N, N-bis (nonafluorobutane sulfonyl)

Lithium hexafluorophosphate: ^Li + PF ₆ ^-
Lithium trifluoromethanesulfonate: CF ₃ SO ₃ ^- Li ⁺
Sodium tetrafluoroborate: ^Na + BF ₄ ^-

<Manufacturing method of dispersant>
(Dispersant 1)
70 parts of methyl methacrylate, 20 parts of t-butyl methacrylate and 10 parts of methacrylic acid were charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., 6.0 parts of 1-thioglycerol was added, and the reaction was carried out for 12 hours. It was confirmed by solid content measurement that 95% had reacted. Next, 8.5 parts of pyromellitic anhydride, 115 parts of propylene glycol monomethyl ether acetate (PGMAc), and 0.20 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU) as a catalyst. Was added and reacted at 100 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. Obtained.

(Dispersant 2)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 25 parts of (3-ethyloxetane-3-yl) methyl methacrylate acrylate, 45 parts of t-butyl methacrylate, 20 parts of methyl methacrylate, and 10 parts of methacrylic acid were placed. It was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., 6.0 parts of 1-thioglycerol was added, and the reaction was carried out for 12 hours. It was confirmed by solid content measurement that 95% had reacted. Next, 8.5 parts of pyromellitic anhydride, 115 parts of propylene glycol monomethyl ether acetate (PGMAc), 1,8-diazabicyclo- [5. 4. 0] -7-Undesen (DBU) 0. Twenty parts were added and reacted at 100 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The non-volatile content was 50% by mass, the acid value was 101 mg KOH / g, and the weight average molecular weight was 90. A dispersant solution 2 of 0 was obtained.

<Manufacturing of coloring compositions for color filters>
[Example 1]
(Coloring Composition DB-1)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours on an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A coloring composition (DB-1) was prepared by filtering with a filter.
Salt-forming compound (D-1): 4.0 parts fine pigment (P-1): 7.0 parts binder resin solution 3: 40.0 parts cyclohexanone: 10.0 parts propylene glycol monomethyl ether acetate (PGMAC)
: 37.0 parts Dispersant solution 2: 2.0 parts

[Examples 2-26, Comparative Examples 1-6]
(Coloring Composition DB-2 to 26, 31 to 36)
Coloring compositions (DB-2 to 26, 31 to 36) were prepared in the same manner as in Example 1 except that the salt-forming compound, the refined pigment, and the binder resin solution were changed to the compositions shown in Table 4.

[Example 27]
(Preparation of DB-27)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours on an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A coloring composition (DB-27) was prepared by filtering with a filter.
Salt-forming compound (D-3): 4.0 parts micronized pigment (P-1): 6.0 parts micronized pigment (P-5): 1.0 parts binder resin solution 3: 45.0 parts cyclohexanone: 10.0 parts Propylene glycol monomethyl ether acetate (PGMAC)
: 33.0 parts Dispersant solution 2: 2.0 parts

[Examples 28 to 30, Comparative Examples 7 to 10]
(DB-28-30, 37-40)
Coloring compositions DB-28-30 and 37-40 were prepared in the same manner as in Example 27 except that the salt-forming compound, the refined pigment, and the binder resin solution were changed to the compositions shown in Table 4.

<Evaluation of coloring composition for color filter>
The obtained coloring composition was evaluated for heat resistance of the coating film as follows. The results are shown in Table 4.

(Evaluation of heat resistance of coating film)
The obtained 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, then dried at 70 ° C. for 20 minutes, and then heated at 220 ° C. for 20 minutes and allowed to cool. By doing so, a coated film substrate was produced. After the heat treatment at 220 ° C., the coating rotation speed of the spin coater was adjusted so that the film thickness of the produced coating film substrate was 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source was measured with a microphotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Measured using. After that, as a heat resistance test, the mixture was heated at 230 ° C. for 1 hour, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , The color difference ΔEab * was calculated. If ΔEab * is less than 3.0, there is no practical problem.
ΔEab * ＝ √ ((L * (2) -L * (1)) 2+ (a * (2) -a * (1)) 2+ (b * (2) -b * (1)) 2)
⊚: ΔEab * is less than 1.0 ○: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

<Manufacturing of photosensitive coloring compositions for color filters>
[Example 31]
(Photosensitive coloring composition (R-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 R-1.
Coloring composition (DB-1): 60.0 parts Binder resin solution 3: 11.0 parts Photopolymerizable monomer: 4.6 parts Dipentaerythritol penta and hexaacrylate ("Aronix M400" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 1.2 parts
1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]
(BASF Japan "Irgacure OXE01")
Cyclohexanone: 5.2 parts propylene glycol monomethyl ether acetate (PGMAC)
: 18.0 copies

[Examples 32 to 60, Comparative Examples 11 to 20]
(Photosensitive coloring composition (R-2 to 40))
Photosensitive coloring compositions (R-2 to 40) were prepared in the same manner as in Example 1 except that the coloring composition and the binder resin solution were changed to the coloring compositions shown in Table 5.

[Comparative Example 21]
(Photosensitive coloring composition (R-41))
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 R-41.
Coloring composition (DB-31): 60.0 parts Binder resin solution 3: 9.0 parts Lithium bis (trifluoromethanesulfonyl) imide
: 0.4 part photopolymerizable monomer: 4.2 part dipentaerythritol penta and hexaacrylate ("Aronix M400" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator: 1.2 parts
1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]
(BASF Japan "Irgacure OXE01")
Cyclohexanone: 5.2 parts propylene glycol monomethyl ether acetate (PGMAC)
: 19.6 copies

<Evaluation of photosensitive coloring composition for color filters>
The obtained photosensitive coloring composition was evaluated for storage stability (foreign matter evaluation) and coating film heat resistance as follows. The results are shown in Table 5.

(Storage stability (foreign matter evaluation))
The coloring composition (R-1 to 37) stored at 10 ° C. for half a year was applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater, and then 20 at 70 ° C. A coating film substrate was prepared by drying for a minute, then heating at 220 ° C. for 30 minutes, and allowing to cool, and the coated film substrate was observed at a magnification of 500 using an optical microscope.
◎: No foreign matter is generated ○: A small amount of foreign matter is observed but usable level ×: A level that is not practical due to a large amount of foreign matter

(Heat resistance of coating film)
The obtained photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 220 ° C. for 30 minutes. A coated substrate was produced by allowing it to cool. After the heat treatment at 220 ° C., the coating rotation speed of the spin coater was adjusted so that the film thickness of the produced coating film substrate was 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source was measured with a microphotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Measured using. After that, as a heat resistance test, the mixture was heated at 230 ° C. for 1 hour, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , The color difference ΔEab * was calculated. If ΔEab * is less than 3.0, there is no practical problem.
ΔEab * ＝ √ ((L * (2) -L * (1)) 2+ (a * (2) -a * (1)) 2+ (b * (2) -b * (1)) 2)
⊚: ΔEab * is less than 1.0 ○: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

As in Examples 31 to 60, a structural unit in which a cationic group having a specific structure and an anion dye are salted in one molecule, and a structural unit in which a cationic group having a specific structure and an anion having a specific structure are salted are used. When the salt-forming compounds contained together were contained, the heat resistance was good in each case. In addition, it was excellent in storage stability, and foreign matter in the coating film was in the range where it could be used as a color filter. On the other hand, Comparative Examples 11 to 20 contain a structural unit obtained by salting a cationic group having a specific structure and an anionic dye in one molecule, but do not contain a structural unit obtained by salting an anion having a specific structure. Since it is a compound, the heat resistance is poor. Further, Comparative Example 21 contains a metal salt or an organic cationic salt of an anion having a specific structure, but is not salted into a resin having a cationic group in the side chain, so that the storage stability is poor and the coating film is coated. There were many foreign substances and it was a level that could not be used as a color filter.

<Making color filters>
A green photosensitive coloring composition used for producing a color filter was prepared in combination with the photosensitive coloring composition of the present invention.

(Preparation of Green Photosensitive Coloring Composition (RG-1))
After stirring and mixing the mixture having the following composition so as to be uniform, the mixture was dispersed for 5 hours on an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5. The mixture was filtered through a 0 μm filter to prepare a green coloring composition (DG-1).
Green pigment (CI Pigment Green 58) 12.0 parts Resin type dispersant (“EFKA4300” manufactured by BASF Japan Ltd.) 1.0 part Binder resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition 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).
Green coloring composition (DG-1) 34.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toa Synthetic Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Japan Ltd.) "Irgacure 907" 2.0 parts sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.) 0.4 parts ethylene glycol monomethyl ether acetate 45.1 parts

(Making a color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (R-3) was applied onto the substrate with a spin coater to a film thickness such that x = 0.640 to form a colored film. The coating film was irradiated with ultraviolet rays of ^{300 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 230 ° C. for 20 minutes to obtain a red filter segment. Was formed. By the same method, the green photosensitive coloring composition (RG-1) is used to form a green filter segment having a thickness of y = 0.600, and then the blue photosensitive coloring composition (R) of the present invention is formed. A blue filter segment was formed with a thickness of −23) so that y = 0.060, and each of them was applied to obtain a color filter.

By using the photosensitive coloring composition of the present invention, the heat resistance of the color filter was improved, and it could be preferably used.

Claims (10)

A coloring composition for a color filter containing at least a colorant, a binder resin and an organic solvent, wherein the colorant is a structural unit represented by the following general formula (1) and the following general formula (2) in one molecule. A coloring composition for a color filter containing a salt-forming compound having a structural unit represented.
General formula (1)

[In the general formula (1), R ¹ represents an alkyl group which may have a hydrogen atom or a substituent. R ^{2 to} R ⁴ 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, and R ² two of to R ⁴ may be bonded to each other to form a ring. Q ¹ is an alkylene group, an arylene group, ^{-CONH-R 5} - or ^{-COO-R 5} - represents, ^{R 5} represents an alkylene group. Y ⁻ represents an anionic dye. ]
General formula (2)

[In the general formula (2), R ⁶ represents an alkyl group which may have a hydrogen atom or a substituent. R ^{7 to} R ⁹ 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, and R ⁷ Two of ~ R ⁹ may be combined with each other to form a ring. Q ² is an alkylene group, an arylene group, ^{-CONH-R 10} - or ^{-COO-R 10} - ^{represents, R 10} represents an alkylene group.
Z ⁻ represents an anion represented by the following general formula (2a), an anion represented by the following general formula (2b), an anion represented by the following general formula (2c), or an anion represented by the following general formula (2d). ]

[In the general formula (2a), R ¹¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and ^{when a plurality of R 11} and H are present, they are the same but different. May be good. c represents an integer of 1 to 6. ]

[In the general formula (2b), R ¹² represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a phenyl group substituted with a cyano group, B represents a boron atom, and Hal represents a halo. It represents a group, when R ^{12, Hal} there are a plurality each of which may be the same or different. d represents an integer of 1 to 4. ]

[In the general formula (2c), R ³¹ and R ³² each independently represent a halogenated hydrocarbon group, a cyano group or _two ^{FSO groups which may be linked by a sulfonyl group, and both R 31} and R ³² are sulfonyl groups. In the case of halogenated hydrocarbon groups which may be linked by a group, they may be bonded to each other to form a ring. However, ^{at least one of R 31} and R ³² is a halogenated hydrocarbon group or a cyano group. ]

[In the general formula (2d), R ¹⁴ represents a halogenated hydrocarbon group that may be linked by a linking group having a nitrogen atom or an oxygen atom. ] The salt-forming compound further has a structural unit having at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetane group, a t-butyl group, an isocyanate group and a (meth) acryloyl group. The coloring composition for a color filter according to claim 1. The coloring composition for a color filter according to claim 2, wherein the salt-forming compound has a structural unit having an oxetane group and a structural unit having a t-butyl group. Any of claims 1 to 3 in which the molar ratio of the structural unit represented by the general formula (1) to the structural unit represented by the following general formula (2) is 2/1 to 1/2 in the salt-forming compound. The coloring composition for a color filter according to item 1. ^{Z −} in the general formula (2) of the salt-forming compound is represented by the anion represented by the following formula (2b-1), the anion represented by the following formula (2c-1), and the following formula (2c-2). The coloring composition for a color filter according to any one of claims 1 to 4, which is at least one anion selected from the group consisting of anions.

The coloring composition for a color filter according to any one of claims 1 to 5, wherein the binder resin contains an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain. The active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is on the side of a copolymer of an unsaturated ethylenic monomer having a carboxyl group and another unsaturated ethylenic monomer. The coloring composition for a color filter according to claim 6, which is a resin obtained by adding an unsaturated ethylenic monomer having an epoxy group to a part of a chain carboxyl group. The coloring composition for a color filter according to any one of claims 1 to 7, wherein the coloring agent further contains an organic pigment. The coloring composition for a color filter according to any one of claims 1 to 8, further containing a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising a filter segment formed from the coloring composition for a color filter according to any one of claims 1 to 9 on a base material.