JP7103054B2 - Coloring compositions for color filters, and color filters - Google Patents

Description

The present invention relates to a coloring composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., and a color filter including a filter segment formed by using the coloring composition. be.

In recent years, liquid crystal display devices have been evaluated for their space saving, light weight, and power saving due to their thinness, and recently, they are rapidly becoming widespread in television applications. For television applications, it is required to further improve the performance such as brightness and contrast, and it is desired that the color filter, which is a member constituting the color liquid crystal display device, further improves the transmittance and the contrast. ing.

As a method for producing a color filter, a dyeing method for dyeing a pattern after forming a pattern with a photoresist, or a pigment-containing resin in which a transparent electrode having a predetermined pattern is formed in advance and dissolved and dispersed in a solvent by applying a voltage is used. Electrodeposition method for ionizing and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material The method is known, and recently, the pigment dispersion method has become the mainstream. However, a color filter using a pigment as a colorant disturbs the degree of polarization controlled by the liquid crystal display due to light scattering by the pigment particles and the like, resulting in a decrease in brightness and contrast of the color liquid crystal display device. There is a problem that it is easy.

As a technique for solving this problem, practical application of a dye-based curable composition using a dye that can exist in a medium of the curable composition as a colorant has been studied and proposed (for example, a patent). Reference 1). However, the dye used in the color resist has problems of heat resistance, light resistance, and solubility in the resin and the organic solvent used for the resin.

Therefore, in order to improve the solubility in an organic solvent, a color filter using a salt-forming compound of a cationic dye and an anionic compound which is a strong acid salt as a colorant has been proposed (Patent Documents 1 to 4). ). In general, it is known that the solubility of a cationic dye in an organic solvent is improved by replacing the counter anion (Cl ⁻ , etc.) of the cationic dye with an anion derived from an anionic compound. However, with the above method, sufficient solubility in the main organic solvent used when producing the color filter cannot be obtained, and compatibility with the resin is poor. Therefore, the long-term storage stability of the coloring composition for the color filter is stable. It is difficult to provide strong adhesion between the coating film and a transparent substrate such as glass, and at the same time, it is difficult to solve important problems in color filters such as solvent resistance and alkali developability of the coating film. could not.

On the other hand, in order to improve heat resistance and light resistance, a coloring composition in which a dye is chemically bonded to a polymer (see Patent Documents 5 to 6), an anionic substituent (-SO _3H , etc.) in a side chain of a cationic dye, etc. A colored composition obtained by salt formation with a polymer having (Patent Document 7) has been proposed. However, the above-mentioned coloring composition has insufficient solvent resistance and resistance, and although the alkali solubility and glass adhesion when used as a color resist agent are improved to some extent, the required levels in recent years can be satisfied. There wasn't.

Japanese Unexamined Patent Publication No. 2013-067776 Japanese Unexamined Patent Publication No. 2012-107192 Japanese Unexamined Patent Publication No. 2012-1733399 Japanese Unexamined Patent Publication No. 2013-163804 Japanese Unexamined Patent Publication No. 2000-162429 Japanese Unexamined Patent Publication No. 2012-032754 Japanese Unexamined Patent Publication No. 2013-137502

INDUSTRIAL APPLICABILITY The present invention can form a coating film suitable for forming a color filter having high storage stability, excellent heat resistance, developability (alkali solubility), and adhesion to a transparent substrate such as glass. An object of the present invention is to provide a coloring composition for a color filter and a color filter.

<1> A coloring composition for a color filter containing a colorant, a binder resin and an organic solvent, wherein the colorant contains a polymer (A) containing at least a repeating unit represented by the following general formula (1). A coloring composition for a color filter, which is a dye to be used.

General formula (1)

[In general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. Y ^- represents a monovalent anionic group.
B ⁺ is a cation derived from a cationic dye and
Z ^- is derived from an anionic compound,
Anion represented by the following general formula (2a),
Anion represented by the following general formula (2b),
It represents 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 ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and when a plurality of R ¹ and H are present, they are the same but different. May be good. c represents an integer from 0 to 6. ]

[In the general formula (2b), R ² 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. When a group is shown and a plurality of ^R2 and Hal are present, they may be the same or different. d represents an integer from 0 to 4. ]

[In general formula (2c), R ³ and R ⁴ 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 ³ and R ⁴ 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 ³ and R ⁴ is a halogenated hydrocarbon group or a cyano group. ]

[In the general formula (2d), R ⁵ represents a halogenated hydrocarbon group that may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

<2> The coloring composition for a color filter according to claim 1, wherein X ⁺ in the general formula (1) is a divalent linking group represented by the following general formula (2) or the following general formula (3). ..

General formula (2)

[In the general formula (2), R ¹⁴ and R ¹⁵ each independently represent a monovalent organic group.
* ¹ represents a bond with R ¹² and * ² represents a bond with R ¹³ . ]

General formula (3)

[In the general formula (3), R ¹⁶ and R ¹⁷ each independently represent a monovalent organic group.
* ¹ represents a bond with R ¹² and * ² represents a bond with R ¹³ . ]

<3> The coloring composition for a color filter according to claim 2, wherein X ⁺ in the general formula (1) is a divalent linking group represented by the general formula (2).

<4> The coloring composition for a color filter according to any one of claims 1 to 3 ^, wherein Y ⁻ in the general formula (1) is −CO _2- ^or SO _3- .

<5> Any one of claims 1 to 4, wherein the dye having a cationic group is at least one dye selected from the group consisting of xanthene dyes, triphenylmethane dyes, cyanine dyes, and squarylium dyes. The coloring composition for a color filter according to the section.

<6> The coloring composition for a color filter according to any one of claims 1 to 5, wherein the coloring agent further contains a pigment.

<7> The coloring composition for a color filter according to any one of claims 1 to 6, further containing at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerization initiator.

<8> A color filter formed by the coloring composition for a color filter according to any one of claims 1 to 7.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to form a coating film suitable for forming a color filter having high storage stability, excellent heat resistance, developability (alkali solubility), and adhesion to a transparent substrate such as glass. Coloring compositions for color filters can be provided. Further, it is possible to provide a high-quality color filter having excellent performance.

The coloring composition for a color filter of the present invention (hereinafter, may be referred to as a coloring composition) contains a coloring agent, a binder resin and an organic solvent, and the coloring agent is at least a repeating unit represented by the general formula (1). It is characterized by containing the polymer (A) having.
Hereinafter, the constituent requirements of the present invention will be described in detail.
In the present application, when "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", or "(meth) acrylate" is described, unless otherwise specified, "(meth) acrylate" is used. It shall represent "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", or "acrylate and / or methacrylate". Further, "CI" mentioned in the present specification means a color index (CI).

<Coloring composition for color filters>
<Colorant>
The colorant in the present invention is a dye containing a polymer (A) containing at least a repeating unit represented by the general formula (1). The polymer (A) containing the repeating unit represented by the general formula (1) has an anion derived from an anionic compound at the cationic moiety of a resin having an amphoteric ion structure having a cationic moiety and an anionic moiety in the same molecule. Z ⁻ has a salt-forming structure in which the cation B ⁺ derived from the cationic dye is selectively co-salted at the anionic site. As a result, it has high storage stability and heat resistance, and also has excellent alkali solubility (developability) and glass adhesion. Further, the colorant may contain other colorants such as organic pigments and dyes.

[Polymer (A) containing a repeating unit represented by the general formula (1)]
General formula (1)

[In general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. Y ^- represents a monovalent anionic group.
B ⁺ is a cation derived from a cationic dye and
Z ^- is derived from an anionic compound,
Anion represented by the following general formula (2a),
Anion represented by the following general formula (2b),
It represents 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 ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and when a plurality of R ¹ and H are present, they are the same but different. May be good. c represents an integer from 0 to 6. ]

[In the general formula (2b), R ² 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. When a group is shown and a plurality of ^R2 and Hal are present, they may be the same or different. d represents an integer from 0 to 4. ]

〔一般式（２ｃ）において、Ｒ^３およびＲ^４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、シアノ基またはＦＳＯ_２基を示し、Ｒ^３およびＲ^４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^３およびＲ^４の少なくとも一つはハロゲン化炭化水素基またはシアノ基である。〕

[In general formula (2c), R ³ and R ⁴ 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 ³ and R ⁴ 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 ³ and R ⁴ is a halogenated hydrocarbon group or a cyano group. ]

[In the general formula (2d), R ⁵ represents a halogenated hydrocarbon group that may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

(R ¹² and R ¹³ : divalent linking group)
As a divalent linking group in the general formula (1) R ¹² and R ¹³ ,
A divalent hydrocarbon group, a group consisting of a combination of a divalent hydrocarbon group and a linking group containing a carbon atom and an atom other than a hydrogen atom, or a part of the hydrogen atom of these groups is substituted with a halo group. Examples can be mentioned. Examples of the halo group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of such a divalent linking group include an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, an arylene alkanediyl group having 7 to 20 carbon atoms, or an arylene alkanediyl group having 1 to 10 carbon atoms. At least one selected from the alkanediyl group and the arylene group having 6 to 20 carbon atoms, and -O-, -S-, -COO-, -CONRb- (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). ) And a group composed of a combination of at least one selected from SO ^2- .

The alkanediyl group having 1 to 10 carbon atoms may be a linear group or a branched chain, for example, a methylene group, an ethylene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2. -Diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane -1,4-diyl group, pentane-1,5-diyl group, hexane-1,5-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group, decan-1,10- Examples thereof include an alkanediyl group having 1 to 10 carbon atoms such as a diyl group.

Examples of the arylene group having 6 to 10 carbon atoms include a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group and the like.

The arylene alcandiyl group is a divalent group formed by combining an arylene group and an alcandiyl group. For example, a phenylene methylene group, a phenylenedi methylene group, a phenylene trimethylene group, a phenylene tetramethylene group and a phenylene pentamethylene group. , Phenylene C _1-6 alcandiyl group such as phenylene hexamethylene group can be mentioned.

Further, at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, and -O-, -S-, -COO-, and -CONRb- (Rb is a hydrogen atom or carbon). The group is selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms as a group formed by combining an alkyl group having numbers 1 to 8) and at least one selected from SO ^2- . A group consisting of a combination of at least one of the above groups and at least one selected from -O-, -COO- and SO ^2- is preferable, and an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms are preferable. A group consisting of a combination of at least one selected from and at least one selected from -O- and SO ^2- is more preferable. Specific examples of the alkyl group having 1 to 8 carbon atoms according to Rb include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a hexyl group. , Heptyl group, octyl group and the like.

As the divalent linking group in R ¹² , an alcandiyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkandiyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms A group consisting of a combination of at least one selected from-O-, -S-, -COO-, -CONRb- and SO ^2- is preferable, and an arylene group having 6 to 10 carbon atoms is preferable. Or at least one selected from an alcandiyl group having 1 to 8 carbon atoms and an arylene group having 6 to 10 carbon atoms and at least one selected from -O-, -COO-, -CONRb- and SO ^2- . The group formed by combining
Of these, -COOCH ₂ CH _2- * and ^-CONHCH ₂ CH _2- * are most preferable as the divalent linking group in R12. * Represents a bond with X ⁺ .

It is preferable that an alkanediyl group having 1 to 10 carbon atoms or an arylene group having 6 to 20 carbon atoms is bonded to X ⁺ .

Further, as the divalent linking group ⁱⁿ R13, an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene alkanediyl group having 7 to 20 carbon atoms is preferable, and the arylene alkanediyl group having 7 to 20 carbon atoms is preferable. The alkanediyl group of ~ 5 is more preferable, and a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group and a pentane-1,5-diyl group are further preferable.

(X ⁺ : cationic divalent linking group)
The cationic divalent linking group in X ⁺ of the general formula (1) is represented by the following general formula (2), the following general formula (3) or P ⁺ (R ²⁰¹ ) (R ²⁰² )-, and the like. Group is mentioned. R ²⁰¹ and R ²⁰² each independently represent a monovalent organic group.

General formula (2)

[In the general formula (2), R ¹⁴ and R ¹⁵ each independently represent a monovalent organic group.
* ¹ represents a bond with R ¹² and * ² represents a bond with R ¹³ . ]

General formula (3)

[In the general formula (3), R ¹⁶ and R ¹⁷ each independently represent a monovalent organic group.
* ¹ represents a bond with R ¹² and * ² represents a bond with R ¹³ . ]

As monovalent organic groups in R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²⁰¹ and R ²⁰² ,
Examples of monovalent hydrocarbon groups include monovalent aliphatic hydrocarbon groups, monovalent alicyclic hydrocarbon groups and monovalent aromatic hydrocarbon groups. It may be either. Further, the monovalent aliphatic hydrocarbon group may be in either a linear form or a branched form, and the monovalent aliphatic hydrocarbon group and the monovalent alicyclic hydrocarbon group are saturated hydrocarbons. It may be a hydrogen group or an unsaturated hydrocarbon group. The position of the unsaturated bond of the unsaturated hydrocarbon group may be either within the molecular chain or at the end of the molecular chain, and can be held at any position. Here, the term "alicyclic hydrocarbon group" as used herein is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. Further, in the present specification, the "aliocyclic hydrocarbon group" and the "aromatic hydrocarbon group" are not only a group consisting of only a ring structure, but also a divalent aliphatic hydrocarbon group is further substituted in the ring structure. It is a concept that also includes the above-mentioned groups, and it is sufficient that at least an alicyclic hydrocarbon or an aromatic hydrocarbon is contained in the structure. Further, the monovalent hydrocarbon group may have a substituent within a range that does not deviate from the gist of the present invention. The position and number of substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. Examples of the substituent include a halo group, a cyano group, a formyl group, a nitro group, a trialkylsilyl group, an alkoxy group, an aryloxy group, a heterocyclic group and the like. Examples of the halo group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the monovalent aliphatic hydrocarbon group include an alkyl group, an alkenyl group and an alkynyl group. The aliphatic hydrocarbon group preferably has 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. Commercially available alkyl groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl. Group, undecyl group, 1-methyldecyl group, dodecyl group, 1-methylundecyl group, 1-ethyldecyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyloctyl group, hexadecyl group, octadecyl group And so on. Commercially available products of alkenyl groups include, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1,3-butadienyl group, 1-pentenyl group, 2-pentenyl group, 1 -Hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like can be mentioned. Commercially available products of alkynyl groups include, for example, ethynyl group, 1-propynyl group, 1-butynyl group, 1-pentynyl group, 3-pentynyl group, 1-hexynyl group, 2-ethyl-2-butynyl group and 2-. Examples thereof include an octynyl group, a (4-ethynyl) -5-hexynyl group, a 2-decynyl group and the like.

Examples of the monovalent alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridging ring hydrocarbon group, a spirohydrocarbon group, a cyclic terpene hydrocarbon group and the like. Can be done. The aliphatic hydrocarbon group preferably has 3 to 30, more preferably 3 to 20, and even more preferably 3 to 12. Examples of commercially available cycloalkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group and the like. , 1-Cyclohexenyl group and the like. Commercially available products of condensed polycyclic hydrocarbon groups include, for example, tricyclodecanyl group, decahydro-2-naphthyl group, adamantyl group and the like, and commercially available products of crosslinked polycyclic hydrocarbon groups include, for example, tricyclo [ 5.2.1.0 <2,6>] Decane-8-yl group, pentacyclopentadecanyl group, isobonyl group, dicyclopentenyl group, tricyclopentenyl group and the like can be mentioned. Further, examples of the spirohydrocarbon group include spiro [3,4] heptane, a monovalent group obtained by removing one hydrogen atom from spiro [3,4] octane, and the like, and examples of the cyclic terpene hydrocarbon group include spiro [3,4] heptane and a monovalent group obtained by removing one hydrogen atom from spiro [3,4] octane. For example, a monovalent group obtained by removing one hydrogen atom from p-menthan, tsujan, karan and the like can be mentioned.

Examples of the monovalent aromatic hydrocarbon group include an aryl group and an aralkyl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. Commercially available aryl groups include, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylene group, an azulenyl group, a 9-fluorenyl group and the like, and examples of the aralkyl group include a benzyl group, a phenethyl group and a trityl group. The group etc. can be mentioned.

The cationic divalent linking group in X ⁺ is preferably a group represented by the general formula (2) or the general formula (3), and more preferably a group represented by the general formula (2). be. Further, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are preferably monovalent aliphatic hydrocarbon groups, more preferably monovalent aliphatic hydrocarbon groups having 1 to 5 carbon atoms, and even more preferably. Is a methyl group or an ethyl group, particularly preferably a methyl group.

(Y- ^: anionic monovalent group)
Examples of the anionic monovalent group in Y ⁻ of the general formula (1) include CO _2- ^, SO _3- ^, H ₂ PO _4- ^, etc., from the viewpoint of availability of raw materials and heat resistance. CO _2- or SO ₃ ^- is preferred ^{, and} SO _3- is particularly preferred.

(Cation derived from cationic dye (B ⁺ ))
As the cationic dye in the cation derived from the cationic dye of the present invention, a cationic dye that ionically bonds with the amphoteric ionic resin that is the precursor of the polymer (A) described above is preferable, and at least one onium base in the molecule. Alternatively, as long as it has an amino group (-NH ₂ , -NHR, -NR ₂ ) in a broad sense, it is not particularly limited, and its solubility in an organic solvent or a developing solution, salt forming property, absorbance, and other substances in the present composition are not particularly limited. It can be appropriately selected in consideration of all the required performances such as interaction with the components of the above, light resistance, and heat resistance.

From the viewpoint of availability, the preferred onium salt structure of the cationic dye is preferably an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt, and a phosphonium salt, and storage stability (thermal stability) is taken into consideration. Then, the ammonium salt, the iodonium salt, and the sulfonium salt are more preferable, and the ammonium salt is more preferable.

Examples of the cationic dye include anthraquinone-based cationic dyes, monoazo-based cationic dyes, disazo-based cationic dyes, oxazine-based cationic dyes, aminoketone-based cationic dyes, and among xanthene-based cationic dyes, rhodamine-based cationic dyes. Examples thereof include quinoline-based cationic dyes, triarylmethane-based cationic dyes, diarylmethane-based cationic dyes, thiazine-based cationic dyes, acrydin-based cationic dyes, azine-based cationic dyes, and methine-based cationic dyes. Specific examples of cationic dyes that can be used for the synthesis of salt-forming compounds are shown below by color index numbers.
Among these cationic dyes, it is preferably a basic dye.

(Basic dye)
The basic dyes used in the coloring composition for a color filter of the present invention include triarylmethane-based basic dyes, xanthene-based basic dyes, preferably rhodamine-based basic dyes, flavin-based basic dyes, and auramine-based basic dyes. . Can be mentioned.

Specifically, as the triarylmethane-based basic dye, C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like can be mentioned. Above all, C.I. I. It is preferable to use Basic Blue 7, Green 4, Violet 1, and Violet 3.
It is also preferable to use a triarylmethane basic dye having the following chemical formula.

(Triarylmethane basic dye 1)

(Triarylmethane basic dye 12)

Further, as a rhodamine-based basic dye, C.I. I. Basic Red 1 (Rhodamine 6G, 6GCP), 3 and 8 (Rhodamine G), C.I. I. Basic Violet 10 (Rhodamine B) and the like can be mentioned. Above all, C.I. I. Basic Red 1 and Violet 10 are preferably used.

Further, as a flavin-based basic dye, C.I. I. Basic Yellow 1, as an auramine-based basic dye, C.I. I. Basic Yellow 2, 3, Safranin-based basic dyes include C.I. I. Basic Red 2, Phloxine-based basic dyes include C.I. I. Basic Red 12, as an acridine-based basic dye, C.I. I. Basic Yellow 5, as an oxazine-based basic dye, C.I. I. Basic Blue 3, thiazine-based basic dyes include C.I. I. Basic Blue 24, as a methine-based basic dye, C.I. I. Basic Red 12, C.I. I. Basic Yellow 11, 21, 28, and methylene blue basic dyes include C.I. I. Basic blue 9 (methylene blue FZ, methylene blue B), 25 (basic blue GO), 24 (new methylene blue NX) and the like can be mentioned. Above all, C.I. I. It is preferable to use Basic Yellow 1, Blue 9, 24, and 25.
It is also preferable to use a methine-based basic dye having the following chemical formula.

(Methine-based basic dye 3)

Examples of the squarylium-based basic dye include (SQ-1K) of JP-A-2017-114956.

Among them, it is preferable to use a triarylmethane-based basic dye, a rhodamine-based basic dye, or a methylene blue-based basic dye in terms of good color development. Further, a flavin-based basic dye as a complementary color is an effective material for forming red pixels. The methylene blue basic dye is a preferable material in that it exhibits a clear blue color and is excellent in heat resistance when made into a salt-forming dye. Further, the flavin-based basic dye is a preferable material in that it exhibits a clear yellowish color and is excellent in heat resistance when it is made into a salt-forming dye.

As the mode of the cationic dye, in addition to the mode of the basic dye, the mode of an oil-soluble dye can also be used. For example, C.I. I. Solvent Red 49 and the like are preferable.

(Anions ( ^Z- ) derived from anionic compounds and represented by the following general formulas (2a) to (2d))
The anions represented by the general formulas (2a) to (2d) derived from the anionic compound in Z ⁻ of the general formula (2) will be described in detail.

(Anion represented by the general formula (2a))

[In the general formula (2a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and when a plurality of R ¹ and H are present, they are the same but different. May be good. c represents an integer from 0 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 ¹ 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. It 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) include (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^２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また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^２、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０～４の整数を示す。〕 (Anion represented by the general formula (2b))

[In the general formula (2b), R ² 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. When a group is shown and a plurality of ^R2 and Hal are present, they may be the same or different. d represents an integer from 0 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 nitro 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 ² of the general formula (2b) is synonymous with the halogenated hydrocarbon group in R ¹ of the general formula (2a) described above. R ² 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 ) 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) ^- , Tetrakiss (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.

(Anion represented by the general formula (2c))

[In general formula (2c), R ³ and R ⁴ 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 ³ and R ⁴ 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 ³ and R ⁴ is a halogenated hydrocarbon group or a cyano group. ]

The halogenated hydrocarbon group in R ³ and R ⁴ of the general formula (2c) is synonymous with the halogenated hydrocarbon group in R ¹ of the general formula (2a) described above. Further, R ³ and R ⁴ may form a cyclic structure of an aliphatic saturated hydrocarbon system. The sulfonyl group in the halogenated hydrocarbon group which may be linked with a sulfonyl group is a linking group of N- ^{and R3} or N- ^{and R4} . R ³ and R ⁴ 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 the anion 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.

(Anion represented by the general formula (2d))

[In the general formula (2d), R ⁵ 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 ⁵ of the general formula (2d) is synonymous with the halogenated hydrocarbon group in R ¹ of the general formula (2a) described above. Halogenated hydrocarbon groups may be linked by -O-, -CO-, -COO-, -CO-NH- or the like.
R ⁵ 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). In addition, specific examples of anions that can be preferably used are shown below.

[Method for producing polymer (A) containing repeating unit represented by general formula (1)]
The polymer (A) containing the repeating unit represented by the general formula (1) can be synthesized by using a known synthesis method. An example of the synthesis method will be described below.
The polymer (A) of the present invention is a solution prepared by dissolving an amphoteric ionic resin which is a precursor of the polymer (A) in water or a water-soluble solvent, and the general formulas (2a) to (2d) of the present application. An anionic compound having an anion (Z ⁻ ) represented by (Z −) and a solution dissolved in water or a water-soluble solvent are mixed and stirred, and then a cationic dye having a cation (B ⁺ ) of the present application is used. It can be easily obtained by dropping a solution dissolved in dissolved water or a water-soluble solvent, mixing and stirring. In the aqueous solution, the cationic group of the amphoteric ionic resin and the specific anion (Z ⁻ ) of the anionic compound of the present application, and the anionic group of the amphoteric ionic resin and the cation of the cationic dye (B ⁺ ) are ionic bonded, respectively. As a result, it becomes water-insoluble and the salt-forming compound is precipitated. The anionic compound and the cationic dye may be used in the reverse order, and the amphoteric resin, the anionic compound, and the cationic dye to be used may be used alone or in multiple types having different structures. You may.

As for the ratio of amphoteric ionic resin: anionic compound: cationic dye, the salt-forming compound of the present invention can be used as long as the molar ratio of the cationic group to the anionic compound in the amphoteric ionic resin is in the range of 10/1 to 1/10. It can be adjusted suitably, and the range of 5/1 to 1/5 is more preferable, and the range of 2/1 to 1/2 is even more preferable. Further, if the molar ratio of the anionic group to the cationic compound in the zwitterionic resin is in the range of 10/1 to 1/10, the salt-forming compound of the present invention can be suitably adjusted, and 5/1 to 1/5. The range is more preferable, and the range of 2/1 to 1/2 is even more preferable.

(Method for producing an amphoteric ion resin which is a precursor of the polymer (A))
The zwitterionic resin, which is a precursor of the polymer (A), can be synthesized by using a known synthetic method. Preferred production methods include the following methods (i) and (ii).
≪Manufacturing method (i) ≫
A method of polymerizing an ethylenically unsaturated monomer (b1), which is a precursor of a repeating unit represented by the general formula (1), and another ethylenically unsaturated monomer (b3) by a known polymerization reaction.

≪Manufacturing method (ii) ≫
An ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4) and another ethylenically unsaturated monomer (b3) are added to an intermediate polymer (a) obtained by a known polymerization reaction. A method for reacting a modified species (b4).
Each manufacturing method will be described below.

≪Manufacturing method (i) ≫
Examples of the ethylenically unsaturated monomer (b1) which is a precursor of the repeating unit represented by the general formula (1) include a monomer represented by the following general formula (4).

(Ethylene unsaturated monomer (b1))
General formula (4)

[In the general formula (4), R ⁴¹ represents a hydrogen atom or a methyl group, R ⁴² and R ⁴³ each independently represent a divalent linking group, and X ⁺ represents the following general formula (5) or It represents a group represented by the general formula (6), and Y ⁻ represents CO ₂ ⁻ or SO ₃ ⁻ . ]

General formula (5)

[In the general formula (5), R ⁵¹ and R ⁵² each independently represent a monovalent organic group. * ¹ represents a bond with R ⁴² , and * ² represents a bond with R ⁴³ . ]

General formula (6)

[In the general formula (6), R ⁶¹ and R ³⁶ each independently represent a monovalent organic group.
* ¹ represents a bond with R ⁴² , and * ² represents a bond with R ⁴³ . ]

The divalent linking group in R ⁴² and R ⁴³ of the general formula (4) is synonymous with the divalent linking group in R ¹² and R ¹³ of the general formula (1).

The monovalent organic group in R ⁵¹ and R ⁵² of the general formula (5) is synonymous with the monovalent organic group in R ²¹ and R ²² of the general formula (2).

The monovalent organic group in R ⁶¹ and R ⁶² of the general formula (6) is synonymous with the monovalent organic group in R ³¹ and R ³² of the general formula (3).

Examples of the compound represented by the general formula (4) include compounds represented by the following (4-1 to 4-24).

Among them, compounds (4-1), (4-2), (4-9), (4-10), (4-11), (4-12), (4-17), (4-18), (4-21), (4-22), (4-23) are preferable, and (4-1), (4-2), (4-9), (4-10), (4-4) are more preferable. 11), (4-12), (4-23), more preferably (4-9), (4-10), (4-11), (4-12), (4-23). Yes, most preferably (4-9), (4-10).

(Other ethylenically unsaturated monomers (b3))
Examples of the other ethylenically unsaturated monomer (b3) include an acrylic monomer, a carboxyl group-containing ethylenically unsaturated monomer, and other monomers.
Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t. -Alkyl (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate;
Alicyclics such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth 9 acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate) Formula alkyl (meth) acrylates;
(Meta) acrylates having heterocyclic substituents such as tetrahydrofurfuryl (meth) acrylates and 3-methyloxetanyl (meth) acrylates;
(Meta) acrylates having aromatic substituents such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethylene oxide modified (meth) acrylate, and paracumylphenoxyethylene oxide modified (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(Meta) acrylamide (In addition, when it is described as "(meth) acrylamide", it means acrylamide and / or methacrylamide. The same shall apply hereinafter), N, N-dimethyl (meth) acrylamide, N, N. Examples thereof include (meth) acrylamides such as-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-couplerolactone-added acrylic acid, ε-couplerolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Acids and the like can be mentioned.

Other monomers include, for example, styrene and styrenes such as α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate can be mentioned.

Other ethylenically unsaturated monomers (b3) can be used alone or in combination of two or more.

≪Manufacturing method (ii) ≫
Examples of the ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4) include a monomer represented by the following general formula (7).

(Ethylene unsaturated monomer (b2))
General formula (7)

[In the general formula (7), R ⁷¹ represents a hydrogen atom or a methyl group, and R ⁷² represents a divalent organic group. Z represents -N (R ⁷³ ) (R ⁷⁴ ), or P (R ⁷⁵ ) (R ⁷⁶ ), or a group represented by the following general formula (8), and R ⁷³ to R ⁷⁶ are independent of each other. Indicates a monovalent organic group. ]

General formula (8)

[In the general formula (8), R ⁸¹ and R ⁸² each independently represent a monovalent organic group. ]

The divalent organic group in R ⁷² of the general formula (7) is synonymous with the divalent linking group in R ¹² of the general formula (1).
The monovalent organic group in R ⁷³ to R ⁷⁶ of the general formula (7) is synonymous with the monovalent organic group in the general formulas (2) and (3).
The monovalent organic group in R ⁸¹ and R ⁸² of the general formula (8) is synonymous with the monovalent organic group in R ³¹ and R ³² of the general formula (3).

The ethylenically unsaturated monomer (b2) represented by the general formula (7) is, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-. Secondary such as dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, 2,2,6,6-tetramethylpiperidyl methacrylate, 1,2,2,6,6-pentamethylpiperidyl methacrylate Or (meth) acrylates having a tertiary amino group;
Tertiary such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. (Meta) acrylamides having an amino group; and the like. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate), N, N-dimethylaminopropyl (meth) acrylamide, 1,2,2,6,6-pentamethyl Piperidyl methacrylate is preferred, and 1,2,2,6,6-pentamethyl piperidyl methacrylate is more preferred.

(Other ethylenically unsaturated monomers (b3))
The other ethylenically unsaturated monomer (b3) is synonymous with the ethylenically unsaturated monomer (b3) in the production method (i).

(Denatured species (b4))
As the modified species (b4), any compound that can react with Z in the general formula (7), which is a constituent monomer of the polymerized intermediate polymer (a), and gives the structure of the general formula (1) after the reaction. The present invention is not particularly limited, and examples thereof include a compound represented by the following general formula (9) and a compound represented by the following general formula (10).

General formula (9) X- (CH ₂ ) _n -Q
[In the general formula (9), X represents a halogen atom, n represents an integer of 1 to 4 ^, and Q represents CO _2- ^, SO _3- ^or PO _4- . ]

General formula (10)

[In general formula (10), R ¹⁰¹ represents carbon or S = O, and n represents an integer of 2 to 6. ]

Examples of the compound represented by the general formula (9) include chloroacetic acid, fluorinated acetic acid, bromoacetic acid, iodoacetic acid, chloropropionic acid, fluorinated propionic acid, bromopropionic acid, iodopropionic acid, chlorobutanoic acid and fluoride. Butanoic acid, bromobutanoic acid, iodobutanoic acid chloromethanesulfonic acid, methylfluorosulfonic acid, bromomethanesulfonic acid, iodomethanesulfonic acid, chloropropanesulfonic acid, propanesulfonic acid fluoride, bromopropanesulfonic acid, iodopropanesulfonic acid, chloro Butane sulfonic acid, butane fluorinated sulfonic acid, bromobutane sulfonic acid, iodobutane sulfonic acid chloromethanephosphonic acid, methyl fluorinated phosphonic acid, bromomethanephosphonic acid, iodomethanephosphonic acid, chloropropanephosphonic acid, propanephosphonic acid fluoride, bromo Propanephosphonic acid, iodopropanephosphonic acid, chlorobutanephosphonic acid, butanefluorinated butanephosphonic acid, bromobutanephosphonic acid, iodobutanephosphonic acid and the like can be mentioned, but bromoacetic acid, chloropropionic acid and chloroacetic acid are preferable, and chloroacetic acid is particularly preferable. Is particularly preferred.

Examples of the compound represented by the general formula (10) include propane sultone, butane sultone, α-acetolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone ε-caprolactone. Of these, propane sultone and butane sultone are preferable.

The molecular weight of the polymer (A) used in the present invention is not particularly limited, but the mass average molecular weight measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, and 3, More preferably 000 to 15,000.

Further, the amphoteric ion resin which is a precursor of the polymer (A) suitable for the present invention 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.

In the amphoteric ionic resin which is a precursor of the polymer (A), the total content of the structural units represented by the above general formula (1) is not particularly limited, but the total structure contained in the polymer (A) is not particularly limited. When the unit is 100% by mass, the total content of the structural unit represented by the above general formula (1) is 5% by mass or more from the viewpoint of solvent solubility and coloring power of the salt-forming compound. It is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. When an appropriate amount is contained, the adhesion to the base material and various durability of the coating film are further improved.

Examples of a method for obtaining an amphoteric ionic resin and an intermediate polymer (a) which are precursors of the polymer (A) containing a repeating unit represented by the general formula (1) suitable for the present invention include anionic polymerization and living anionic polymerization. Known methods such as cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization can be used. Of these, free radical polymerization or living radical polymerization is preferable.

<Other colorants>
The coloring composition of the present invention may be used in combination with a coloring agent (pigment / dye) other than the salt-forming compound as long as the effect of the present invention is not impaired, for the purpose of adjusting the chromaticity.

[Pigment]
The coloring composition for a color filter of the present invention can be used as a coloring composition for a color filter by further adding a pigment. 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 coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 97, 122, 123, 146, 149, 150, 168, 169, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, Red pigments such as 286 or 287 can be used. Further, the red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and the like orange pigments and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, Yellow pigments such as 181 and 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231 can be used in combination.

Examples of the green coloring composition for forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63 and other green pigments can be used. 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. Further, for the green coloring composition, 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, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231 can be used in combination.

Examples of the blue coloring composition for forming the blue filter segment include C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: Blue pigments such as 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. Can be used. Further, the blue coloring composition includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and other purple pigments can be used in combination. 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.

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. Pigment Red 144, 146, 177, 169, 81 and other purple and red pigments can be used alone or in admixture. 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.

Other colorants can be used alone or in combination of two or more.

<Pigment miniaturization>
When the colorant used in the coloring composition for a color filter of the present invention is a pigment, it is preferable to use it in a finely divided form from the viewpoint of contrast. The miniaturization method is not particularly limited, and examples thereof include wet grinding, dry grinding, and dissolution / precipitation method. Among these, the salt milling treatment by the kneader method, which is one of the wet grinding methods, is preferable. The average primary particle size determined by the TEM (transmission electron microscope) of the pigment is preferably 5 to 90 nm, more preferably 10 to 70 nm. Having an appropriate particle size improves the dispersibility and further improves the contrast ratio.

The salt milling treatment is a batch type or continuous type of a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, a sand mill, and a planetary mixer. This is a treatment in which a water-soluble inorganic salt and a water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Of these, inexpensive sodium chloride (salt) is preferable. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment.

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

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

<Dye derivative>
The coloring composition for a color filter of the present invention can arbitrarily select and contain various conventionally known dye derivatives. Examples of the dye derivative include a compound in which an organic pigment, anthraquinone, acrydone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent. No. 63-305173, No. 57-15620, No. 59-40172, No. 63-17102, No. 5-9469, No. 2001-335717, No. 2003-2003. 128669, 2003-167112, 2004-091497, 2004-307854, 2007-156395, 2008-094873, 2008-094986. The ones described in Japanese Patent Application Laid-Open No. 2008-905007, Japanese Patent Application Laid-Open No. 2008-195916, Japanese Patent Application Laid-Open No. 4585781, and the like can be used, but the present invention is not limited thereto. The dye derivative may be added at the time of pigmentation such as salt milling treatment, or may be added at the time of dispersion.

<Binder resin>
The binder resin is a compound required for film formation. Examples of the binder resin include a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin having an ethylenically unsaturated double bond. It is also preferable that the active energy ray-curable resin has thermosetting property. The binder resin is preferably an alkali-soluble resin from the viewpoint of developability.

The content of the binder resin in the coloring composition of the present invention is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is contained, film formation becomes easy and good color characteristics can be easily obtained.

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.

The alkali-soluble resin is a resin having an acidic group such as a carboxyl group and a sulfone group. The alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene /. (Anhydrous) maleic anhydride copolymer and the like can be mentioned. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer having more improved heat resistance and transparency are preferable, and an acrylic resin having an acidic group is more preferable.

It is preferable to use an active energy ray-curable resin having an ethylenically unsaturated active double bond in order to impart photoreactivity to the alkali-soluble resin. As a result, the solvent resistance of the cured film is further improved.

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 anhydride or a tetracarboxylic acid dianhydride such as pyromellitic 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 ethylenic double bond is used as the polybasic acid anhydride, the unsaturated ethylenic 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 the 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) acrylates to which (poly) 12-hydroxystearic acid and the like are 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 thereto. However, two or more types can be used together.

The mass 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 mass 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.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with a thermoplastic resin which is a binder resin. Thermosetting compounds include, for example, epoxy compounds and / or resins, oxetane compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins. Examples include melamine compounds and / or resins, urea compounds and / or resins, phenolic compounds and / or resins.

<Organic solvent>
The organic solvent is used to assist the dispersion of the colorant and to appropriately adjust the viscosity of the coloring composition.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-. 1,3-Propanediol, 3,5,5-trimethyl-2-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, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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 mono Methyl 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 cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Vortic acetate, dibasic acid ester and the like.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl are good because of the good dispersibility and permeability of the colorant and the applicability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol, diacetone alcohol and 3-methoxybutanol, and ketones such as cyclohexanone.

The colorant can be used alone or in combination of two or more.

Further, the organic solvent can be used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant because the coloring composition can be adjusted to an appropriate viscosity and a colored film having a desired uniform film thickness can be formed. Is preferable.

<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 that may be added to the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin.

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.

The photopolymerizable compound can be used alone or in combination of two or more.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is blended, the photocurability and developability are further improved.

<Photopolymerization initiator>
The coloring composition for a color filter of the present invention may contain a photopolymerization initiator. This facilitates photocuring when the filter segments are formed by the photolithography method. The blending amount of the photopolymerization initiator is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, based on 100 parts by mass of the colorant. When an appropriate amount is blended, the photocurability and developability are further improved.

Photopolymerization initiators include, for example, 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-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetphenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzophenone, Benzophenones such as benzoin 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 Benzophenone compounds such as'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6 -Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4 Triazine compounds such as -trichloromethyl- (4'-methoxystyryl) -6-triazine; 1- (N-4-benzoylphenyl-carbazole-3-yl) -butane-1 , 2-dione-2-oxime-O-acetate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4') -Oxime ester compounds such as methoxy-naphthyl) ethylidene) hydroxylamine; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9 , 10-Phenanthrene quinone, camphorquinone, ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanosen compounds are used.

The photopolymerization initiator can be used alone or in combination of two or more.

The amount used for the photopolymerization initiator is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, based on 100 parts by mass of the colorant. When used in an appropriate amount, photocurability and developability are further improved.

<Sensitizer>
In the coloring composition, a photopolymerization initiator and a sensitizer can be used in combination.
The sensitizer includes, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone. Polymethine dyes such as derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, aclysine 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 Derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrilium derivatives, tetraphyllin derivatives, anurene derivatives, spiropyrane derivatives, spiroxazine derivatives, thiospiropyrane derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy Esters, acylphosphine oxides, methylphenylglioxylates, benzyls, 9,10-phenanthrene quinones, camphorquinones, ethyl anthraquinones, 4,4'-diethylisophthalophenones, 3,3'or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.

In addition, Makoto Okawara et al. "Dye Handbook" (1986, Kodansha), Makoto Okawara et al. "Chemistry of Functional Dyes" (1981, CMC), Chuzaburo Ikemori et al. The sensitizer described in CMC) can be mentioned.

The sensitizer can be used alone or in combination of two or more.

The amount of the sensitizer used is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, based on 100 parts by mass of the photopolymerization initiator. When used in an appropriate amount, photocurability and developability are further improved.

<Amine compounds>
The coloring composition may contain an amine compound. Amine compounds can reduce dissolved oxygen.

Amine-based compounds include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, Examples thereof include 2-ethylhexyl 4-dimethylaminobenzoate and N, N-dimethylparatoluidine.

<Leveling agent>
The coloring composition may contain a leveling agent. As a result, the coatability is further improved, and the surface smoothness of the coating film is further improved.
Leveling agents include, for example, in addition to dimethylsiloxane, various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic-based surfactants, and cationic-based (surfactants, anionic surfactants, etc.). Can be mentioned.
The dimethylsiloxane is preferably a dimethylsiloxane having a polyether structure and / or a polyester structure in the main chain. Commercially available products of dimethylsiloxane having a polyether structure in the main chain are FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2207, and Big Chemie manufactured by Toray Dow Corning. BYK-333 manufactured by the company and the like can be mentioned. Examples of commercially available products of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie.

Anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, and so on. Examples thereof include triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and the like.

Examples of the chaotic surfactant 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.

The leveling agent can be used alone or in combination of two or more.

The content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the coloring composition.

<Epoxy compound>
The coloring composition can contain an epoxy compound.

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

Commercially available phenol novolac type epoxy resins include, for example, Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC Corporation, and D.D., manufactured by Dow Chemical Corporation. E. Examples thereof include N438, RE-306 manufactured by Nippon Kayaku Corporation, jER152 and jER154 manufactured by Mitsubishi Chemical Corporation.

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

Examples of commercially available products 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.

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

Commercially available products of bisphenol type epoxy resin are jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide, 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, bisphenol-F type epoxy resin such as YDF-8170 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., etc. Can be mentioned.

Commercially available products of biphenol type epoxy resin include biphenol type epoxy resin such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Corporation, and bixylenol type epoxy resin such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation. Can be mentioned.

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

Examples of commercially available products of the naphthalene skeleton-containing epoxy resin include NC-77000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd. and EXA-4750 manufactured by DIC Corporation.

Examples of commercially available alicyclic epoxy resins include Seikiside 2021P, 2081, 2000, Epolide PB3600, PB4700, GT401, EHPE-3150, and Cyclomer M100 manufactured by Daicel Corporation.

Examples of commercially available heterocyclic epoxy resins include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

The epoxy compound can be used alone or in combination of two or more.

The content of the epoxy compound is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the coloring composition. When an appropriate amount is contained, the heat resistance is further improved.

<Oxetane compound>
The coloring composition can contain an oxetane compound. Examples of the oxetane compound include compounds having an oxetane group monofunctional, bifunctional, and trifunctional or higher.

Compounds with a monofunctional oxetane group include, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 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. Examples of commercially available products include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Compounds having a bifunctional oxetane group include, for example, 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) -Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, Ethylene glycosbis (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-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-oxetanylmethyl) ether and the like can be mentioned. Examples of commercially available products include OXBP and OXTP manufactured by Ube Corporation, OXT-121 and OXT-221 manufactured by Toagosei Corporation.

Compounds having a trifunctional or higher oxetane group include, for example, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl). -3-oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-) Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrax (3-ethyl-3-oxetanylmethyl) ether, resin containing oxetane radicals Examples thereof include polymers obtained by radical polymerization of (meth) acrylic monomers such as (for example, oxetan-modified phenol novolac resin described in Patent No. 3783462) and OXE-30 described above.

The oxetane compound can be used alone or in combination of two or more.

The content of the oxetane compound is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the coloring composition. When an appropriate amount is contained, the heat resistance is further improved.

<Curing agent, curing accelerator>
The color composition may contain a curing agent and a curing accelerator in order to assist the curing of the thermosetting resin.
Examples of the curing agent include phenolic resins, amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, and sulfonic acid-based compounds. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine-based curing agents are preferable.
The curing accelerator is, for example, an amine compound (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, imidazole, etc.) 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-methacryloyl). Oxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxy Ethyl-S-triazine, isocyanuric acid adduct, etc.) and the like.

The curing agent and the curing accelerator can be used alone or in combination of two or more.

The amount of the curing agent and the curing accelerator used is preferably 0.01 to 15% by mass with respect to 100 parts by mass of the thermosetting resin, respectively.

<UV absorber>
The coloring composition may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

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. Highly compatible with light sensitivity and resolution. When the 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 non-volatile 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.

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) Mix of -2H-benzotriazole-2-yl) phenyl] propionate, 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)- Compounds of 4-hydroxy, C7-9 side chain and linear alkyl ester, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- ( Examples thereof include 2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol.

Commercially available products are 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. and the like.

The triazine-based organic compound is, for example, 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol, 2- [4,6-yl]. 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.

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

Benzophenone-based organic compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulphonic acid-3 water temperature, 2-hydroxy-4-n. -Octoxybenzophenone, 2,2-di-hydroxy-4-methoxybenzophenone and the like can be mentioned.

Commercially available products are "KEMISORB 10", "KEMISORB 11", "KEMISORB 11S", "KEMISORB 12", "KEMISORB 111" manufactured by Chemipro Kasei Co., Ltd., "SEESORB 101", "SEESORB 107" manufactured by ADEKA Corporation. Examples thereof include "ADEKA STUB 1413".

<Thiol chain transfer agent>
The coloring composition can contain a thiol-based chain transfer agent. When a thiol-based chain transfer agent is used together with a photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates chile radicals that are less susceptible to polymerization inhibition by oxygen, so that photosensitivity is improved. As a result, the photocurability from the surface of the coating film to the deep part of the coating film is further improved.

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tristrimercaptopropionate (2-Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine Examples thereof include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10%, more preferably 2 to 8%, based on 100% by mass of the non-volatile content of the coloring composition. When an appropriate amount is used, the light sensitivity is improved and a film having a good shape can be obtained.

<Antioxidant>
The coloring composition of the present invention may contain an antioxidant. The antioxidant can suppress the film formed from the coloring composition from being oxidized and yellowed by a heating step such as thermosetting, and can maintain the transmittance of the film. In particular, when the colorant concentration of the photosensitive coloring composition is high, the cross-linking component is relatively small. Therefore, if measures such as using a highly sensitive cross-linking component or increasing the amount of the photopolymerization initiator are taken, yellowing of the thermal process will occur. This is to become stronger. 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 absorbing function, a radical catching function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenol-based or a hindered amine-based antioxidant. , 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.

As hindered phenolic antioxidants, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-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.
Commercially available products are ADEKA's ADEKA STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320, Chemipro's KEMIOX101, 179, 76, 9425, BASF's IRGANOX1010, 1035, 1076, 1098, 1135. , 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sianox CY-1790, CY-2777 manufactured by Sun Chemical Co., Ltd. and the like.

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 can be mentioned. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.
Commercially available products are ADEKA's ADEKA STAB 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-3549, UV- made by Sun Chemical Co., Ltd. 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) diphosphyte, 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.
Examples of commercially available products include ADEKA's ADEKA TAB PEP-36, PEP-8, HP-10, ADEKA TAB 2112, 1178, 1500, C, 3013, TPP, BASF's IRGAFOS 168, and Clariant Chemicals' Hostanox P-EPQ.

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.
Examples of commercially available products include 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.
Commercially available products are ADEKA's ADEKA STAB LA-29, LA-31RG, LA-32, LA-36, -412S, Chemipro Kasei's KEMISORB71, 73, 74, 79, 279, BASF's TINUVIN PS, 99-2. , 384-2, 900, 928, 1130 and the like.

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.
Examples of commercially available products 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.
Examples of commercially available products 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 non-volatile content of the coloring composition because the spectral characteristics and sensitivity are good.

<Other additives>
The coloring composition of the present invention may contain a storage stabilizer as another additive in order to stabilize the viscosity of the composition over time. In addition, 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 amount of the storage stabilizer used is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

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 amount of the adhesion improver used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5% by mass, based on 100 parts by mass of the colorant.

<Manufacturing method of coloring composition>
The coloring composition of the present invention contains, for example, a mixture containing a dye containing a polymer (A) containing a repeating unit represented by the general formula (1), a binder resin, and an organic solvent, for example, three roll mills and two. It is preferably produced by finely dispersing using various dispersion means such as a roll mill, a sand mill, a kneader, or an attritor. Further, when a plurality of colorants are used, the coloring composition of the present invention can be produced by separately preparing dispersions and then mixing these dispersants. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, the above-mentioned fine dispersion step is performed. It does not have to be. When the mixture contains a pigment, it is preferable to use a dispersion aid such as a pigment derivative in combination.

When the coloring composition is used as a resist material, it is preferably prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkali-developed coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersion aids, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

When dispersing the colorant in the coloring composition, a dye derivative, a dispersant (for example, a resin-type dispersant), a dispersion aid (for example, a surfactant) and the like 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 color filter having high spectral transmittance can be obtained. The dye derivative is as described above.

<Dispersant>
(Resin type dispersant)
The resin-type dispersant has a colorant-affinitive portion having a property of adsorbing to the colorant and a portion compatible with a component other than the colorant. Resin-type dispersants include, for example, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and poly. Siloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, salts thereof, etc. Water-soluble such as oil-based dispersant, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples thereof include resins, water-soluble polymer compounds, polyester-based materials, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.

As the dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, such as a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, and a nitrogen-containing heterocycle. A nitrogen atom-containing acrylic block copolymer and a urethane-based polymer dispersant having a functional group containing the above are preferable.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemie Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc. 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, manufactured by BASF. 4,300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno's Ajispa-PA111, PB711, PB821, PB822, PB824 and the like are preferable.

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 tricarboxylic acid anhydride and / or 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 tricarboxylic acid anhydride and / or 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 the 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. In addition, 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.

The dispersant can be used alone or in combination of two or more.

The amount of the dispersant used is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount is used, the film forming property is further improved.

<Dispersion aid>
(Surfactant)
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as 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.

The dispersion aid can be used alone or in combination of two or more.

The amount of the dispersion aid used is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, based on 100 parts by mass of the colorant. Dispersibility is further improved when an appropriate amount is used.

<Removal of coarse particles>
The colored composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed 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 preferably includes a substrate and a red filter segment, a green filter segment, and a blue filter segment. The color filter can also further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment. In the color filter of the present invention, at least one of a red filter segment, a green filter segment, and a yellow filter segment is preferably formed using the coloring composition of the present invention, and a green filter segment may be formed. More preferred.

<Manufacturing method of color filter>
The color filter can be produced by a printing method, a photolithography method, or the like, and the photolithography method is preferable.

A photolithography method is preferable for forming the filter segment. The photolithography method uses, for example, a coating method such as spray coating, spin coating, slit coating, or roll coating on a transparent substrate on a photosensitive coloring composition prepared as a solvent-developed or alkali-developed colored resist. Then, the coating is applied so that the dry film thickness is 0.2 to 10 μm. The coating is exposed to ultraviolet light through a mask having a predetermined pattern.

After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern. In addition, it can be heated as needed to accelerate the polymerization of the filter segments and black matrix formed by development. The photolithography method can form filter segments with higher accuracy than the printing method.

Examples of the development include aqueous alkali developers such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine, triethanolamine and tetramethylammonium hydroxide. In addition, a defoaming agent or a surfactant can be used as the developing solution. Examples of the developing processing method include a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid filling) developing method, and the like.

In order to increase the exposure sensitivity to ultraviolet rays, a water-soluble or alkali-soluble resin (for example, polyvinyl alcohol, water-soluble acrylic resin, etc.) can be formed on the resist film formed from the photosensitive coloring composition. This makes it possible to prevent oxygen that inhibits UV curing of the resist film.

Examples of the substrate include glass plates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminum borosilicate glass; resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate. Further, it is preferable that the surface of the substrate is provided with a transparent electrode made of indium oxide, tin oxide or the like for driving the liquid crystal display after panelization. When the color filter is used as a solid-state image sensor, the substrate is preferably a silicon wafer. The substrate includes a transparent substrate and a reflective substrate depending on the application.

The thickness of the substrate is about 0.01 to 3 mm.

The film thickness of the filter segment is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. A drying process can be performed during coating. Examples of the drying device include a vacuum dryer, a convection oven, an IR oven, a hot plate and the like.

If a black matrix is formed in advance before forming the filter segment on the substrate, the contrast of the display panel can be further enhanced. As the black matrix, for example, 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. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed thereafter. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the brightness can be improved.
An overcoat film or a transparent conductive film can be formed on the color filter, if necessary.

In the color filter of the present invention, a sealant is used to bond the liquid crystal display to the opposing substrate, liquid crystal is injected from the injection port provided in the seal portion, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by sticking it on the outside of the. This color liquid crystal display is Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Opticary Convencend Bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as).

In addition to the color liquid crystal display device, the color filter of the present invention can also be used for manufacturing a color image pickup device, an organic EL display device, electronic paper, and the like.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment primary particles. Next, for 100 or more pigment particles, the volume (mass) of each particle was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was defined as the average primary particle size.

(Mass average molecular weight of binder resin and dispersant)
The mass average molecular weight (Mw) of the resin is converted to polystyrene measured by using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120 GPC) equipped with an RI detector and using THF as a developing solvent. It is the mass average molecular weight (Mw).

(Acid value of binder resin and dispersant)
The resin acid value is a value obtained by converting the measured acid value (mgKOH / g) into a non-volatile content in accordance with the potentiometric titration method of JIS K 0070.

(Molecular weight of polymer A and intermediate polymer (a))
For the number average molecular weight (Mn) and mass average molecular weight (Mw) of the polymer A, HLC-8320GPC (manufactured by Toso Co., Ltd.) was used as an apparatus, SUPER-AW3000 was used as a column, and 30 mM triethylamine and 10 mM LiBr were used as eluents. It is a polystyrene-equivalent number average molecular weight (Mn) and mass average molecular weight (Mw) measured using an N, N-dimethylformamide solution.

(Amine values of polymer A and intermediate polymer (a))
The amine value of the basic resin type dispersant is a value obtained by converting the measured total amine value (mgKOH / g) into a non-volatile content in accordance with the method of ASTM D 2074.

<Manufacturing of binder resin solution>
(Binder resin solution 1)
70.0 parts of methoxypropyl acetate was placed in 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., and the inside of the reaction vessel was replaced with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) from the dropping tube. , 2,2'-Azobisisobutyronitrile 0.4 parts mixture 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 mass average molecular weight of 26,000. 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 methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40%. To prepare a binder resin solution 1.

(Binder resin solution 2)
370 parts of methoxypropyl acetate 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 the dropping tube was used. , Paracumylphenol ethyleneoxide 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 parts of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the non-volatile 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 resin 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 methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40%. The binder resin solution 2 was prepared. The mass average molecular weight (Mw) was 19,000.

<Manufacturing of finely divided pigments>
(Red refined pigment (P-1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of 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 fine 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 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 red fine 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. did. 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))
A quinophthalone-based yellow pigment represented by the following formula (7) was synthesized according to Japanese Patent Application Laid-Open No. 2012-226110.

Equation (7)

120 parts of the quinophthalone-based yellow pigment represented by the above 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. did. This mixture is put 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 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-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 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-8) was obtained. The average primary particle size of the obtained pigment was 25.4 nm.

(Purple refined pigment (P-9))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 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 90 ° C. for 18 hours. This mixture is put 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. The mixture was dried to obtain 118 parts of a purple fine pigment (P-9). The average primary particle size of the obtained pigment was 26.4 nm.

<Manufacturing of dispersant>
(Dispersant solution 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 measuring the non-volatile content 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. The dispersant solution 1 having a non-volatile content of 50%, an acid value of 100 mgKOH / g, and a mass average molecular weight of 9,000. Got

(Dispersant solution 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 measuring the non-volatile content that 95% of the reaction occurred. 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. The dispersant solution 2 having a non-volatile content of 50%, an acid value of 101 mgKOH / g, and a mass average molecular weight of 9,000. Got

(Dispersant solution 3)
BASF's "EFKA4300" was adjusted with propylene glycol monomethyl ether acetate so that the non-volatile content was 50%. This was designated as the dispersant solution 3.

<Manufacturing of polymer (zwitterionic resin) having a betaine structure in the side chain>
(Polymer J-1)
100 parts of isopropyl alcohol 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-port flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then isopropyl alcohol 50. , N, N-dimethylaminoethyl methacrylate 15 parts, methyl methacrylate 40 parts, t-butyl acrylate 30 parts, 2-hydroxyethyl methacrylate 10 parts, methacrylic acid 5 parts, and 2,2'-azobisisobutyro A mixed solution of 6.0 parts of nitrile was added dropwise over 2 hours, and the mixture was polymerized for 2 hours while maintaining this temperature. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of the polymer intermediate (j-1). Subsequently, 11.7 parts of 1,3-propane sulton was put into the above container, and the reaction was continued at 80 ° C. for 6 hours, and the reaction was terminated when the non-volatile amine value disappeared. 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 isopropyl alcohol was added to the previously synthesized resin solution so that the non-volatile content was 30%. A polymer (J-1) solution having a betaine structure in the side chain was prepared.

(Preparation of polymers J-2 to J-20)
A polymer (J-2)-(J-20) solution having a betaine structure in the side chain was obtained in the same manner as the polymer (J-1) except that the raw materials were changed to those shown in Table 1.

The abbreviations in Table 1 are shown below.
DMAEMA: 2- (dimethylamino) ethyl methacrylate DEAEMA: 2- (diethylamino) ethyl methacrylate DMAPMA: 2- (dimethylamino) propyl methacrylate LA82: 1,2,2,6,6-pentamethyl-4-methacrylic acid -Piperidyl MMA: Methyl methacrylate t-BA: t-Butyl methacrylate HEMA: 2-Hydroxyethyl methacrylate MAA: OXMA methacrylate: (3-Ethyloxetane-3-yl) Methyl methacrylate MOI-BM: 2-Methacrylic acid (0- [1'-Methylpropylideneamino] carboxyamino) ethyl

<Production of a polymer having only a cationic group in the side chain>
(Polymer JH-C)
100 parts of isopropylalcohol was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable 4-port flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then isopropylalcohol 50 , 15 parts of dimethylaminoethylmethyl chloride salt, 40 parts of methyl methacrylate, 30 parts of t-butyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 5 parts of methacrylic acid, and 2,2'-azobisisobutyro. A mixed solution of 6.0 parts of nitrile was added dropwise over 2 hours, and the mixture was polymerized for 2 hours while maintaining this temperature. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of a comparative polymer (JH-1) having a mass average molecular weight of 7,000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and isopropyl alcohol was added to the previously synthesized resin solution so that the non-volatile content was 30%. A polymer (JH-C) solution having only a cationic group in the side chain was prepared.

<Production of a polymer having only an anionic group in the side chain>
(Preparation of polymer JH-A)
100 parts of isopropylalcohol was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable 4-port flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then isopropylalcohol 50 , 15 parts of acrylamide t-butyl sulfonic acid, 40 parts of methyl methacrylate, 30 parts of t-butyl acrylate, 10 parts of 2-hydroxyethyl methacrylate, 5 parts of methacrylic acid, and 6 parts of 2,2'-azobisisobutyronitrile. A mixture of 0.0 parts was added dropwise over 2 hours, and the mixture was polymerized for 2 hours while maintaining this temperature. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of the comparative polymer (JH-2) having a mass average molecular weight of 7,000. 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 propyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 30%. A comparative polymer (JHA) solution having only an anionic group in the side chain was prepared.

The abbreviations in Table 2 are shown below.
DMCMA: Dimethylaminoethylmethyl chloride salt ATBS: Acrylamide t-butylsulfonic acid MMA: Methyl methacrylate t-BA: t-Butyl acrylate HEMA: 2-Hydroxyethyl methacrylate MAA: Methacrylic acid

<Manufacturing of dye containing polymer (A)>
(Dye containing polymer (A-1))
In 39.0 parts of a polymer (J-1) solution having a betaine structure in the side chain, 2.79 parts of bis (trifluoromethanesulfonyl) imide lithium: 2.79 parts (anion equivalent, represented by the above formula (2c-1)) Structure) was added, 117.0 parts of methanol was added, and the mixture was stirred at room temperature to dissolve it. 780.0 parts of water was added dropwise thereto over 60 minutes while stirring at room temperature, and after the completion of the dropping, the mixture was further stirred at room temperature for 60 minutes. Then C.I. I. 4.44 parts of Basic Violet 10 (cation conversion, structure represented by the following formula (B-1)) is dissolved in 222.0 parts of water, and this is added dropwise to the above reaction solution over 60 minutes with stirring at room temperature. After the completion of the dropping, the mixture was further stirred at room temperature for 60 minutes. It was determined that the co-produced salt 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 is performed, and after washing with water, the co-produced salt compound remaining on the filter paper is dried by removing water with a dryer, and the polymer (J-1) having a betaine structure on the side chain and bis ( A dye containing a polymer (A-1) which is a co-salt compound with trifluoromethanesulfonyl) imidelithium and basic violet 10 was obtained.

(Dyes containing polymers (A-2) to (A-58))
Hereinafter, the side chain is the same as that of A-1, except that the polymer (J) having a betaine structure, the cationic dye (B), and the anionic compound (Z) are changed to those shown in Table 3. Polymers (A-2) to polymers (A-58), which are co-salt compounds of a polymer (J) having a betaine structure in a chain and a cationic dye (B) and an anionic compound (Z). The dye to be contained was produced.

Equation (SQ-1K)

Equation B-6

Equation B-9

<Production of salt-forming compound of cationic polymer and anionic compound (Z)>
(Salt-forming compound (AHC-1))
920 parts of water was added to 46 parts of the polymer (JH-C) solution, and the mixture was stirred at room temperature for 60 minutes. Next, 2.80 parts of bis (trifluoromethanesulfonyl) imide lithium: (anion equivalent, structure represented by the formula (2c-1)) was dissolved in 140 parts of water, and this was dissolved in the above reaction solution in the above reaction solution at room temperature for 60 minutes. The mixture was hung and dropped, and after the dropping was completed, the mixture was further stirred at room temperature for 60 minutes. It was judged 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 is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing water with a dryer, and a single salt-forming product of the polymer JH-C and trifluoromethanesulfonyl) imide lithium. AHC-1 was obtained.

(Salt-forming compounds (AHC-2 to AHC-5))
Hereinafter, salt-forming compounds AHC-2 to AHC-5 containing the anionic compound (Z) alone were prepared in the same manner as AHC-1 except that the anionic compound (Z) was changed to that shown in Table 4.

<Production of salt-forming compound of anionic polymer and cationic dye (B)>
(Salt-forming compound (AHA-1))
920 parts of water was added to 46 parts of the polymer (JH-A) solution, and the mixture was stirred at room temperature for 60 minutes. Then C.I. I. 10: 4.44 parts of basic violet (cation conversion, structure represented by formula (B-1)) is dissolved in 222 parts of water, and this is added dropwise to the above reaction solution over 60 minutes with stirring at room temperature. After completion, the mixture was further stirred at room temperature for 60 minutes. It was judged 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 the polymer JHA and C.I. I. An independent salt product AHA-1 with Basic Violet 10 was obtained.

(Salt-forming compounds (AHA-2 to AHA-5))
Hereinafter, the salt-forming compounds AHA-2 to AHA-5 using the cationic dye (B) alone were prepared in the same manner as in AHA-1 except that the cationic dye (B) was changed to that shown in Table 5.

<Manufacturing of coloring compositions for color filters>
[Example 1]
(Coloring Composition CP-1)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-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 (CP-1) was prepared by filtering with a filter.
Dye containing polymer (A-1): 4.0 parts Micronized pigment (P-1): 7.0 parts Binder resin solution 1: 40.0 parts Cyclohexanone: 10.0 parts Propylene glycol monomethyl ether acetate ( PGMAc)
: 37.0 parts Dispersant solution 1: 2.0 parts

[Examples 2-82]
(Coloring Compositions CP-2 to 82, 101, 102)
The coloring composition (the coloring composition was the same as in Example 1 except that the polymer (A), the finely divided pigment (P), the dispersant solution, and the binder resin solution were changed to the compositions shown in Tables 6-1 and 6-2. CP-2 to CP-82) were prepared.

[Comparative Example 1]
(Coloring Composition CPH-1)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-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 (CPH-1) was prepared by filtering with a filter.
Salt-forming compound (AHC-1): 2.0 parts Salt-forming compound (AHA-1): 2.0 parts Fine pigment (P-1): 7.0 parts Binder resin solution 1: 40.0 parts Cyclohexanone: 10.0 parts PGMAc: 37.0 parts Dispersant solution 1: 2.0 parts

[Comparative Examples 2 to 10]
(Coloring Compositions CPH-2 to CPH-10)
The coloring composition was the same as in Comparative Example 1 except that the salt-forming compound (AHC), the salt-forming compound (AHA), the fine pigment (P), the dispersant solution, and the binder resin solution were changed to the compositions shown in Table 7. (CPH-2 to CPH-10) were prepared.

<Evaluation of coloring composition for color filter>
The obtained colored composition was subjected to coating film heat resistance and storage stability (foreign matter evaluation) as follows. The results are shown in Tables 6-1 and 6-2 and Table 7.

(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 230 ° C. for 20 minutes and allowed to cool. By doing so, a coated substrate was produced. After the heat treatment at 230 ° C., the coating rotation speed of the spin coater was adjusted so that the film thickness of the produced coated substrate became 2.0 μm. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the obtained coating film with a C light source. 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 problem in practical use. That is, a rating of 3 or less is a level unsuitable for practical use.
ΔEab ^* = √ ((L ^* (2) -L ^* (1)) ² + (a ^* (2)-a ^* (1)) ² + (b ^* (2)-b ^* (1)) ² )
6: ΔEab ^* is less than 1.0 5: ΔEab ^* is 1.0 or more and less than 2.0 4: ΔEab ^* is 2.0 or more and less than 3.0 3: ΔEab ^* is 3.0 or more and 4.0 Less than 2: ΔEab ^* is 4.0 or more, less than 5.0 1: ΔEab ^* is 5.0 or more

(Storage stability (foreign matter evaluation))
The coloring composition stored for half a year under a cold storage condition of 10 ° C. 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 220 ° C. A coated substrate was prepared by heating and allowing to cool for 30 minutes, and the coated substrate was observed at a magnification of 500 using an optical microscope and visually evaluated. A rating of 3 or less, which requires a processing step, is a level unsuitable for practical use.
6: No foreign matter is generated 5: Very little foreign matter is generated 4: Slightly foreign matter is generated (level that does not cause any problem in use)
3: Generation of foreign matter is observed (a level that can be completely removed by filtration, etc., but is not suitable for practical use)
2: The generation of foreign matter is noticeable (difficult to completely remove by filtration etc., impractical level)
1: Very much foreign matter is generated (impractical level)

<Manufacturing of photosensitive coloring compositions for color filters>
[Example 83]
(Photosensitive coloring composition (CR-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 CR-1.
Coloring composition (CP-1) solution: 60.0 parts Binder resin solution 2: 11.0 parts Photopolymerizable monomer 1: 3.6 parts Dipentaerythritol penta and hexaacrylate (Toagosei Co., Ltd. "Aronix M402"")
Photopolymerizable monomer 2: 1.0 part trimethylolpropane PO-modified triacrylate ("Aronix M310" manufactured by Toagosei Co., Ltd.)
Photopolymerization Initiator 1: 0.6 parts Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime)
(BASF Japan "Irgacure OXE02")
Photopolymerization Initiator 2: 0.6 parts 1- (N-4-benzoylphenyl-carbazole-3-yl) -butane-1,2-dione-2-oxime-O-acetatecyclohexanone: 5.2 parts PGMAc : 18.0 copies

[Examples 84 to 164, Comparative Examples 11 to 20]
(Photosensitive coloring compositions (CR-2 to CR-82, CRH-1 to CRH-10))
Photosensitive coloring compositions (CR-2 to CR-82, CRH-1 to CRH-10) were prepared in the same manner as in Example 83 except that the coloring compositions were changed to the coloring compositions shown in Tables 8 and 9. Made.

<Evaluation of photosensitive coloring composition for color filters>
The obtained photosensitive coloring composition was evaluated for coating film heat resistance, storage stability, developability, and glass adhesion as follows. The results are shown in Tables 8 and 9.

(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 230 ° C. for 20 minutes and allowed to cool. By doing so, a coated substrate was produced. After the heat treatment at 230 ° C., the coating rotation speed of the spin coater was adjusted so that the film thickness of the produced coated substrate became 2.0 μm. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the obtained coating film with a C light source. 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 problem in practical use. That is, a rating of 3 or less is a level unsuitable for practical use.
ΔEab ^* = √ ((L ^* (2) -L ^* (1)) ² + (a ^* (2)-a ^* (1)) ² + (b ^* (2)-b ^* (1)) ² )
6: ΔEab ^* is less than 1.0 5: ΔEab ^* is 1.0 or more and less than 2.0 4: ΔEab ^* is 2.0 or more and less than 3.0 3: ΔEab ^* is 3.0 or more and 4.0 Less than 2: ΔEab ^* is 4.0 or more, less than 5.0 1: ΔEab ^* is 5.0 or more

(Storage stability)
The initial viscosity of the obtained photosensitive coloring composition at 25 ° C. was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Subsequently, after storing in a thermostat at 40 ° C. for 2 weeks and accelerating with time, the viscosity after aging is measured by the same method as the viscosity measurement, and the rate of change in viscosity before and after storage at 40 ° C. for 2 weeks is calculated. Then, the evaluation was performed according to the following criteria. A rating of 3 or less is a level unsuitable for practical use.
6: Viscosity change rate is ± 3% or less 5: Viscosity change rate is more than ± 3% and ± 5% or less 4: Viscosity change rate is more than ± 5% and ± 10% or less 3: Viscosity change rate is ± 10% Exceeding ± 20% or less 2: Viscosity change rate exceeds ± 20% and ± 30% or less 1: Viscosity change rate exceeds ± 30%

(Developability evaluation)
The photosensitive 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, and heated in a clean oven at 70 ° C. for 15 minutes to remove the solvent to obtain a coating film. .. Subsequently, using an ultra-high pressure mercury lamp, ultraviolet exposure was performed with an integrated light intensity of 200 mJ / cm ² , and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. At this time, the time during which the pattern could be formed without remaining development was defined as the development dissolution time, and evaluation was performed according to the following criteria. A rating of 3 or less is a level unsuitable for practical use.
6: Development dissolution time less than 25s 5: Development dissolution time 25s or more and less than 30s 4: Development dissolution time 30s or more and less than 40s 3: Development dissolution time 40s or more and less than 60s 2: Development dissolution time 60s or more and less than 80s 1: When the pattern does not peel off and remain even if the development dissolution time is 80 s or more or less than 80 s

(Evaluation of glass adhesion)
A substrate obtained by applying a photosensitive coloring composition on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed at which the film thickness after drying becomes 2 μm is dried at 70 ° C. for 20 minutes. Ultraviolet rays of 150 mJ / cm ² were irradiated using an ultrahigh pressure mercury lamp through a photomask having 100 openings of 10 μm × 10 μm. Then, it was spray-developed with an alkaline developer consisting of a 0.2% aqueous sodium carbonate solution to remove an unexposed portion, and then washed with ion-exchanged water. At this time, the adhesion was evaluated based on how many patterns of 10 μm × 10 μm remained. Moreover, the developability evaluation was judged according to the following criteria. A rating of 3 or less is a level unsuitable for practical use.
6: 95 or more patterns remain 5: 90-95 patterns remain 4: 80-89 patterns remain 3: 70-79 patterns remain 2:50 ~ 69 patterns remain 1: 50 or less patterns

<Making color filters>
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (CR-29) 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 ultrahigh pressure mercury lamp via a photomask. Next, the unexposed portion was removed by spray development with an alkaline developer consisting of a 0.2% aqueous sodium carbonate solution, washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment. Formed. Then, by the same method, a green filter segment is formed to a film thickness such that y = 0.600 using the green photosensitive coloring composition (CR-32), and further, by the same method, the blue photosensitive coloring composition is formed. A blue filter segment was formed with a thickness of the substance (CR-27) so that y = 0.060, and each of them was applied to obtain a color filter.

By using the coloring composition of the present invention, the heat resistance of the color filter is improved, the developability and the glass adhesion are also good, and other physical properties can be suitably used without any problem.

Claims (8)

A coloring composition for a color filter containing a colorant, a binder resin and an organic solvent, wherein the colorant is a dye containing a polymer (A) containing at least a repeating unit represented by the following general formula (1). There is a coloring composition for a color filter.
General formula (1)

[In general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. Y ⁻ represents a monovalent anionic group.
B ⁺ is a cation derived from a cationic dye and
Z ^- is derived from an anionic compound,
Anion represented by the following general formula (2a),
Anion represented by the following general formula (2b),
It represents 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 ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and when a plurality of R ¹ and H are present, they are the same but different. May be good. c represents an integer from 0 to 6. ]

[In the general formula (2b), R ² 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. When a group is shown and a plurality of ^R2 and Hal are present, they may be the same or different. d represents an integer from 0 to 4. ]

[In general formula (2c), R ³ and R ⁴ 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 ³ and R ⁴ 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 ³ and R ⁴ is a halogenated hydrocarbon group or a cyano group. ]

[In the general formula (2d), R ⁵ represents a halogenated hydrocarbon group that may be linked by a linking group having a nitrogen atom or an oxygen atom. ]
The coloring composition for a color filter according to claim 1, wherein X ⁺ in the general formula (1) is a divalent linking group represented by the following general formula (2) or the following general formula (3).
General formula (2)

[In the general formula (2), R ¹⁴ and R ¹⁵ each independently represent a monovalent organic group.
* ¹ represents a bond with R ¹² and * ² represents a bond with R ¹³ . ]
General formula (3)

[In the general formula (3), R ¹⁶ and R ¹⁷ each independently represent a monovalent organic group.
* ¹ represents a bond with R ¹² and * ² represents a bond with R ¹³ . ] The coloring composition for a color filter according to claim 2, wherein X ⁺ in the general formula (1) is a divalent linking group represented by the general formula (2). The coloring composition for a color filter according to any one of claims 1 to 3 ^, wherein Y ⁻ in the general formula (1) is −CO _2- ^or SO _3- . The present invention according to any one of claims 1 to 4, wherein the dye having a cationic group is at least one dye selected from the group consisting of xanthene dyes, triphenylmethane dyes, cyanine dyes, and squarylium dyes. Coloring composition for color filters. The coloring composition for a color filter according to any one of claims 1 to 5, wherein the coloring agent further contains a pigment. The coloring composition for a color filter according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of a photopolymerizable monomer and a photopolymerization initiator. A color filter formed by the coloring composition for a color filter according to any one of claims 1 to 7.