JP2019109490A - Colored composition for color filter, and color filter - Google Patents

Abstract

To provide a colored composition for a color filter capable of forming a coating film suitable for forming a color filter with high storage stability and excellent heat resistance property, developability (alkali solubility) and adhesion to a transparent substrate such as glass and provide a color filter.SOLUTION: The colored composition for a color filter contains coloring agent, binder resin and organic solvent. The coloring agent is dye which at least contains a polymer (A) including a repeating unit represented by a general formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a coloring composition for a color filter used in the manufacture of a color filter used in a color liquid crystal display device, a color image pickup tube device and the like, and a color filter provided with a filter segment formed using the same. is there.

  In recent years, the liquid crystal display device has been evaluated for its space saving property, light weight property, and the like because of its thinness, and recently, its spread to television applications is rapidly advancing. In television applications, it is required to further improve performance such as brightness and contrast, and in the color filter which is a member constituting a color liquid crystal display device, further improvement of the transmittance and enhancement of the contrast etc. are desired. ing.

  As a method for producing a color filter, after forming a pattern with a photoresist, a staining method for dyeing a pattern, or a transparent electrode having a predetermined pattern is formed in advance, and a pigment-containing resin dissolved or dispersed in a solvent by voltage application is used. Ionization and pattern formation electrodeposition method, offset printing etc. using ink containing thermosetting resin or ultraviolet curing resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material The law, etc. are known, and in recent years, the pigment dispersion method has become mainstream. However, a color filter using a pigment as a coloring agent disturbs the degree of polarization controlled by the liquid crystal due to light scattering by the pigment particles and the like, and as a result, the brightness and contrast of the color liquid crystal display device are lowered. There is a problem that it is easy.

  As a technology to solve this problem, the practical application of a dye-based curable composition using a dye that can be present in a state of being dissolved in a medium of the curable composition has been studied and proposed (for example, a patent) Reference 1). However, dyes used for color resist agents have the problems of heat resistance, light resistance, and solubility in resins and organic solvents used in resins.

Then, in order to improve the solubility to the organic solvent, the color filter which used the salt formation compound of the cationic dye and the anionic compound which is a strong acid salt as a coloring agent is proposed (patent documents 1-4) ). In general, it is known that the solubility of a cationic dye in an organic solvent is improved by substituting the counter anion (Cl ^- or the like) of the cationic dye with an anion derived from an anionic compound. However, the above method can not obtain sufficient solubility with respect to the main organic solvents used at the time of color filter production, and also has poor compatibility with the resin, so long-term storage stability of the coloring composition for color filter At the same time 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 important 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 (refer to Patent Documents 5 and 6) or an anionic substituent (-SO ₃ H etc.) A colored composition (Patent Document 7) formed by forming a salt with a polymer having the However, although the above-mentioned coloring composition has insufficient solvent resistance and resistance, and improves the alkali solubility and the glass adhesion to some extent when used as a color resist agent, it can meet the recent requirement level. It was not.

JP, 2013-067776, A JP 2012-107192 A JP 2012-173399 A JP, 2013-163804, A JP 2000-162429 A JP 2012-032754 A JP, 2013-137502, A

  The present invention is capable of forming a coating film having high storage stability and having excellent heat resistance, developability (alkali solubility), adhesion to a transparent substrate such as glass, and the like and forming a color filter. It is an object of the present invention to provide a color composition for color filter and a color filter.

It is a coloring composition for color filters containing a <1> coloring agent, binder resin, and an organic solvent, Comprising: The said coloring agent contains the polymer (A) containing the repeating unit represented by following General formula (1) at least And a coloring composition for color filters.

General formula (1)

[In the 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 ^- is a monovalent anionic group.
B ⁺ is a cation derived from a cationic dye,
Z ⁻ is derived from an anionic compound,
An anion represented by the following general formula (2a),
An 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, Hal represents a halo group, and when a plurality of R ¹ and Hal are present, they may be the same or different. It is also good. c shows the integer of 0-6. ]

[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 And R ² and Hal may be the same or different when there are a plurality of groups. d shows the integer of 0-4. ]

[In general formula (2c), R ³ and R ⁴ each independently represent a halogenated hydrocarbon group which may be linked by a sulfonyl group, a cyano group or a FSO ₂ group, and R ³ and R ⁴ are both sulfonyl When it is a halogenated hydrocarbon group which may be linked by a group, it may combine with 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 which may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

The coloring composition for color filters 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 to R ¹² and * ² represents a bond to 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 to R ¹² and * ² represents a bond to R ¹³ . ]

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

<4> The Y in the general formula (1) ^- is, -CO ₂ ^- or SO ₃ ^- for a color filter coloring composition according to any one of claims 1 to 3, a.

The dye having a <5> 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 color filters as described in a term.

The coloring composition for color filters of any one of Claims 1-5 in which the <6> above-mentioned coloring agent contains a pigment further.

The coloring composition for color filters of any one of Claims 1-6 which contain at least 1 sort (s) chosen from the group which consists of a <7> and also a photopolymerizable monomer and a photoinitiator.

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

  According to the present invention, it is possible to form a coating film having high storage stability and having excellent heat resistance, developability (alkali solubility), adhesion to a transparent substrate such as glass and forming a color filter. It is possible to provide a coloring composition for color filters. In addition, it is possible to provide a high quality color filter which is excellent in the above-mentioned performance.

The coloring composition for color filters of the present invention (hereinafter sometimes referred to as coloring composition) contains a colorant, a binder resin and an organic solvent, and the colorant is a repeating unit represented by at least the general formula (1) And a polymer (A) having
The constituent features of the present invention will be described in detail below.
In the present application, when it is described as “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, or “(meth) acrylate”, unless otherwise specified, Acryloyl and / or methacryloyl "," acrylic and / or methacrylic "," acrylic acid and / or methacrylic acid ", or" acrylate and / or methacrylate "are intended to mean. In addition, “CI” listed in the present specification means a color index (CI).

<Coloring composition for color filter>
<Colorant>
The coloring agent 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 a repeating unit represented by the general formula (1) is an anion derived from an anionic compound at the cationic site of a resin having a zwitterionic structure having a cationic site and an anionic site in the same molecule. Z ^- has a salt forming structure cation B ⁺ and is selectively Kyozoshio from cationic dye anionic part. As a result, high storage stability, heat resistance, and excellent effects on alkali solubility (developability) and glass adhesion are generated. The colorant may also contain other colorants such as organic pigments and dyes.

[Polymer (A) Containing Repeating Unit Represented by General Formula (1)]
General formula (1)

[In the 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 ^- is a monovalent anionic group.
B ⁺ is a cation derived from a cationic dye,
Z ⁻ is derived from an anionic compound,
An anion represented by the following general formula (2a),
An 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, Hal represents a halo group, and when a plurality of R ¹ and Hal are present, they may be the same or different. It is also good. c shows the integer of 0-6. ]

[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 And R ² and Hal may be the same or different when there are a plurality of groups. d shows the integer of 0-4. ]

〔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 which may be linked by a sulfonyl group, a cyano group or a FSO ₂ group, and R ³ and R ⁴ are both sulfonyl When it is a halogenated hydrocarbon group which may be linked by a group, it may combine with 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 which may be linked by a linking group having a nitrogen atom or an oxygen atom. ]

(R ¹² and R ¹³ : divalent linking group)
The divalent linking group of the general formula ^{(1) R 12} and ^{R 13,}
A divalent hydrocarbon group, a group formed by combining a divalent hydrocarbon group with a linking group containing an atom other than a carbon atom and a hydrogen atom, or a part of the hydrogen atoms of these groups are substituted with a halo group And the like. In addition, as a halo group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
As such a divalent linking group, for example, 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 And at least one member selected from alkanediyl groups and arylene groups having 6 to 20 carbon atoms, and -O-, -S-, -COO-, -CONRb- (wherein R b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) And a group formed by combining at least one selected from SO ^{2 2-} and the like.

  The alkanediyl group having 1 to 10 carbon atoms may be linear or branched and, for example, methylene group, ethylene group, ethane-1,1-diyl group, propane-1,1-diyl group, 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, decane-1,10- The C1-C10 alkanediyl groups, such as a diyl group, can be mentioned.

As a C6-C10 arylene group, a phenylene group, a naphthylene group, a biphenylene group, an anthrylene group etc. can be mentioned.

The arylenealkanediyl group is a divalent group formed by combining an arylene group and an alkanediyl group, and examples thereof include phenylenemethylene group, phenylenedimethylene group, phenylenetrimethylene group, phenylenetetramethylene group, and phenylenepentamethylene group. , it may be mentioned phenylene C _1-6 alkanediyl group such as phenylene hexamethylene group.

In addition, 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-, -CONRb- (Rb is a hydrogen atom or carbon indicates the number 1-8 alkyl group.), and as is in combination with at least one group selected from SO ^2-, selected from the alkanediyl group and arylene group having 6 to 20 carbon atoms having 1 to 10 carbon atoms And a group formed by combining at least one selected from at least one selected from -O-, -COO-, and SO ^2-, and is preferably an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms. More preferred is a group formed by combining at least one selected from: and at least one selected from -O- and SO ^2- . In addition, the specific example of a C1-C8 alkyl group which concerns on Rb is a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert- butyl group, a hexyl group, for example And heptyl and octyl groups.

Examples of the divalent linking group for R ^12, an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms or alkanediyl group and arylene group having 6 to 20 carbon atoms having 1 to 10 carbon atoms, and at least one selected from, -O -, - S -, - COO -, - CONRb- and ^SO group comprising a combination of at least one selected from ^2-is preferable, an arylene group having 6 to 10 carbon atoms Or at least one selected from an alkanediyl 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- Is more preferably a group formed by combining, and particularly preferably a group formed by combining an alkanediyl group having 1 to 8 carbon atoms and -COO- or CONRb- A.
Among ^them, the divalent linking group for _{^{R 12, -COOCH 2 CH 2 -}} *, - CONHCH 2 CH 2 - * is most preferred. * Represents a bond with X ⁺ .

In addition, it is preferable that a C1-C10 alkanediyl group or a C6-C20 arylene group couple | bonds with X ^<+> .

^As the divalent linking group for ^{R 13,} an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or is arylene alkanediyl group having 7 to 20 carbon atoms is preferable, a carbon number 1 An alkanediyl group of 5 to 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 more preferable.

(X ⁺ : cationic divalent linking group)
The cationic divalent linking group represented by X ⁺ in the general formula (1) is represented by the following general formula (2), the following general formula (3) or P ⁺ (R ²⁰¹ ) (R ²⁰² )-, etc. Group is mentioned. Each of R ²⁰¹ and R ²⁰² independently represents 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 to R ¹² and * ² represents a bond to 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 to R ¹² and * ² represents a bond to R ¹³ . ]

As a monovalent organic group in R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²⁰¹ and R ²⁰² ,
Examples thereof include monovalent hydrocarbon groups, and examples of such monovalent hydrocarbon groups include monovalent aliphatic hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups. It may be any. The monovalent aliphatic hydrocarbon group may be either linear or branched, and the monovalent aliphatic hydrocarbon group and the monovalent alicyclic hydrocarbon group may be saturated hydrocarbon. 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 in the molecular chain or at the end of the molecular chain, and may be at any position. Here, in the present specification, “alicyclic hydrocarbon group” is a concept excluding an aliphatic hydrocarbon group having no cyclic structure. Further, in the present specification, “alicyclic hydrocarbon group” and “aromatic hydrocarbon group” mean not only a group consisting of only a ring structure, but also the ring structure having a divalent aliphatic hydrocarbon group further substituted. It is a concept that also includes the above-mentioned groups, as long as at least alicyclic hydrocarbon or aromatic hydrocarbon is contained in the structure. The monovalent hydrocarbon group may have a substituent within the scope of the present invention. The position and number of substituents are arbitrary, and when two or more substituents are included, 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. As a halo group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned.

  As a monovalent | monohydric aliphatic hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group is mentioned, for example. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 12. Commercial products of the alkyl group are, 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, decyl Group, undecyl group, 1-methyl decyl group, dodecyl group, 1-methyl undecyl group, 1-ethyl decyl group, tridecyl group, tetradecyl group, tert-dodecyl group, pentadecyl group, 1-heptyl octyl group, hexadecyl group, octadecyl group Etc. can be mentioned. Commercial products of the alkenyl group 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 And -hexenyl group, 2-ethyl-2-butenyl group, 2-octenyl group, (4-ethenyl) -5-hexenyl group, 2-decenyl group and the like. 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, 2- The octynyl group, the (4-ethynyl) -5-hexynyl group, the 2-decynyl group etc. can be mentioned.

  Examples of monovalent alicyclic hydrocarbon groups include cycloalkyl groups, cycloalkenyl groups, fused polycyclic hydrocarbon groups, bridged ring hydrocarbon groups, spiro hydrocarbon groups, cyclic terpene hydrocarbon groups and the like. Can. The carbon number of the aliphatic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, and still more preferably 3 to 12. Commercial products of the cycloalkyl group include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, t-butylcyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and commercial products of cycloalkenyl group are, for example, And 1-cyclohexenyl group. Further, commercially available products of fused polycyclic hydrocarbon groups include, for example, tricyclodecanyl group, decahydro-2-naphthyl group, adamantyl group and the like, and commercially available products of bridged ring hydrocarbon groups are, for example, tricyclo 5.2.1.0 <2,6>] decane-8-yl group, pentacyclopentadecanyl group, isobonyl group, dicyclopentenyl group, tricyclopentenyl group etc. are mentioned. Furthermore, as the spiro hydrocarbon group, for example, spiro [3,4] heptane, a monovalent group obtained by removing one hydrogen atom from spiro [3,4] octane and the like can be mentioned, and as the cyclic terpene hydrocarbon group, for example, For example, a monovalent group in which one hydrogen atom has been removed from p-menthane, tsujian, curan and the like can be mentioned.

  As a monovalent | monohydric aromatic hydrocarbon group, an aryl group, an aralkyl group, etc. can be mentioned, for example. The carbon number of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Commercial products of the aryl group include, for example, phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenylene group, azulenyl group, 9-fluorenyl group and the like, and examples of the aralkyl group include benzyl group, phenethyl group and trityl group. And the like.

The cationic divalent linking group represented by X ⁺ is preferably a group represented by General Formula (2) or General Formula (3), and more preferably a group represented by General Formula (2) is there. Also, 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 still more preferably Is a methyl group or an ethyl group, particularly preferably a methyl group.

(Y ^-: anionic monovalent group)
The monovalent group of the anionic _in, ^CO 2 - ^- Y of the general formula (1), SO ₃ ^- or _H 2 PO ₄ ^- and others as mentioned, from the viewpoint of availability and heat resistance of the material, CO ₂ ^- or SO ₃ ^- are preferred, SO ₃ ^- is particularly preferable.

(Cation derived from cationic dye (B ⁺ ))
The cationic dye in the cation derived from the cationic dye of the present invention is preferably a cationic dye which is ionically bound to a zwitterionic resin which is a precursor of the polymer (A) described above, and at least one onium base in the molecule There is no particular limitation as long as it has an amino group (-NH ₂ , -NHR, -NR ₂ ) in a broad sense, and solubility in organic solvents and developers, salt formation, absorbance, and others in the present composition It can select suitably in consideration of all the required performances, such as the interaction with the component of, light resistance, heat resistance, etc.

The preferred onium salt structure in the cationic dye is preferably an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt, and a phosphonium salt from the viewpoint of availability etc., and in consideration of storage stability (heat stability) The ammonium salt, the iodonium salt and the sulfonium salt are more preferable, and the ammonium salt is more preferable.

Examples of the cationic dyes include anthraquinone cationic dyes, monoazo cationic dyes, disazo cationic dyes, oxazine cationic dyes, aminoketone cationic dyes, xanthene cationic dyes, rhodamine cationic dyes, and the like. Quinoline-based cationic dyes, triarylmethane-based cationic dyes, diarylmethane-based cationic dyes, thiazine-based cationic dyes, acridine-based cationic dyes, azine-based cationic dyes, methine-based cationic dyes, and the like. Hereinafter, specific examples of cationic dyes that can be used for the synthesis of salt forming compounds are shown by color index numbers.
Among these cationic dyes, an embodiment of a basic dye is preferred.

(Basic dye)
The basic dyes used in the coloring composition for color filters 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 Safranin basic dyes, phloxine basic dyes, thiazine basic dyes, acridine basic dyes, azine basic dyes, methine basic dyes, methylene blue basic dyes, squarylium basic dyes, etc. It can be mentioned.

Specifically, triarylmethane-based basic dyes include C.I. Basic Violet 1 (methyl violet), 3 (crystal violet), 14 (Magenta), C.I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victor Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green), etc. may be mentioned. Among them, C.I. I. It is preferable to use basic blue 7, green 4, violet 1 and violet 3.
Further, it is also preferable to use a triarylmethane basic dye of the following chemical formula.

(Triarylmethane-based basic dye 1)

(Triarylmethane-based basic dye 12)

As rhodamine-based basic dyes, C.I. Basic Red 1 (rhodamine 6G, 6GCP), 3, 8 (rhodamine G), C.I. I. Basic Violet 10 (rhodamine B) and the like. Among them, C.I. I. Basic Red 1 and Violet 10 are preferably used.

Moreover, as a flavin based basic dye, C.I. Basic Yellow 1 As the auramine-based basic dye, C.I. Basic Yellow 2, 3 As the safranin-based basic dyes, C.I. Basic Red 2 As the phloxine-based basic dye, C.I. Basic Red 12; Examples of acridine-based basic dyes include C.I. Basic Yellow 5 As the oxazine-based basic dye, C.I. Basic Blue 3 As the thiazine-based basic dye, C.I. Basic Blue 24. Examples of methine-based basic dyes include C.I. I. Basic Red 12, C.I. Basic Yellow 11, 21, and 28; and methylene blue basic dyes such as C.I. I. Basic Blue 9 (methylene blue FZ, methylene blue B), 25 (basic blue GO), 24 (new methylene blue NX) and the like. Among them, C.I. I. Basic Yellow 1, Blue 9, Blue 24, and Blue 25 are preferably used.
Moreover, it is also preferable to use the methine type basic dye of the following chemical formula.

(Methine basic dye 3)

Moreover, as a squarylium series basic dye, (SQ-1K) of Unexamined-Japanese-Patent No. 2017-114956 etc. is mentioned.

Among them, it is preferable to use a triarylmethane based basic dye, a rhodamine based basic dye, and a methylene blue based basic dye in terms of good color developability. Further, in forming a red pixel, a flavin based basic dye as a complementary color is an effective material. The methylene blue basic dye is a preferable material in that it exhibits a clear blue color and is excellent in heat resistance when used as a salt forming dye. Further, flavin based basic dyes are preferred materials in that they exhibit clear yellowishness and are excellent in heat resistance when used as salt forming dyes.

  As an aspect of the cationic dye, in addition to the aspect of the basic dye, an aspect of an oil-soluble dye can also be used. For example, C.I. I. Solvent Red 49 etc. are preferred.

(Anions (Z ⁻ ) represented by the following general formulas (2a) to (2d) derived from an anionic compound)
The anion represented by General Formula (2a)-(2d) derived from an anionic compound in Z < ^- > of General formula (2) is demonstrated in detail.

(Anion represented by General Formula (2a))

[In the general formula (2a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halo group, and when a plurality of R ¹ and Hal are present, they may be the same or different. It is also good. c shows the integer of 0-6. ]

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

The halogenated hydrocarbon group for R ¹ in 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 a fluorinated alkyl group or a fluorinated aryl It is a group. More preferably, it is a fluorinated aryl group, and particularly preferably a pentafluorophenyl group.

Representative examples of the anion represented by the general formula (2a) include, for example, (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 -, ( nC ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] _{3 PF 3, (n-C} 4 F 9) 2 PF 4 -, (n-C 4 F 9) 3 PF 3 -, (C 2 F 4 H) (CF 3) 2 PF 3 -, (C 2 F ^{_{3 H 2) 3 PF 3 -}} , (C 2 F 5) (CF 3) 2 PF 3 - , and the like. Among them, PF ₆ ⁻ , (C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , (n-CF ₇ ) ₃ PF ₃ ⁻ , (nC ₄ F ₉ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CFCF _{2 2} PF ₄ ^- is preferred.

〔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 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 And R ² and Hal may be the same or different when there are a plurality of groups. d shows the integer of 0-4. ]

  Hal in the general formula (2b) has the same meaning as Hal in the above-mentioned general formula (2a).

R ² represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a cyano group, and as the halogenated hydrocarbon group, halogenated carbon as Z ⁻ in the above-mentioned general formula (1) The halogenated hydrocarbon groups 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, and is preferably a fluorinated alkyl group or a fluorinated aryl group.

The halogenated hydrocarbon group in R ² of the general formula (2b) has the same meaning as the halogenated hydrocarbon group in R ¹ of the general formula (2a) described above. R ² is preferably a halogenated hydrocarbon group, and is preferably a fluorinated alkyl group or a fluorinated aryl group.

Representative examples of the anion represented by the general formula (2b) include, for example, (CF ₃ ) ₄ B ⁻ , CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , ( C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B ( ^{_{CN) 3 F -, (CF}} 3) 3 B (CN) -, (CF 3) 2 B (CN) 2 -, (C 2 F 5) 3 B (CN) -, _{C 2 F 5) 2 B (} CN) 2 -, (n-C 3 F 7) 3 B (CN) -, (n-C 4 F 9) 3 B (CN) -, (n-C 4 F 9 ) ₂ B (CN) ₂ ⁻ , (nC 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 (C) ^{_{CN) 2 -, (CH 2}} CH 2 C 3 F 7) 2 B (CN) 2 -, (n-C 3 F 7 CH 2) 2 B (CN) 2 -, (C 6 H 5) 3 B ( CN) ^- , tetrakis (pentafluorophenyl) borate anion, etc. are mentioned. 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 General Formula (2c))

[In general formula (2c), R ³ and R ⁴ each independently represent a halogenated hydrocarbon group which may be linked by a sulfonyl group, a cyano group or a FSO ₂ group, and R ³ and R ⁴ are both sulfonyl When it is a halogenated hydrocarbon group which may be linked by a group, it may combine with 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 in the general formula (2c) has the same meaning as the halogenated hydrocarbon group in R ¹ of the general formula (2a) described above. Further, R ³ and R ⁴ may form an aliphatic saturated hydrocarbon cyclic structure. The sulfonyl group in the halogenated hydrocarbon group which may be linked by a sulfonyl group is a linking group of N ⁻ and R ³ or N ⁻ and R ⁴ . R ³ and R ⁴ are each independently preferably a halogenated hydrocarbon group linked by a sulfonyl group, more preferably a fluorinated alkylsulfonyl group or a fluorinated arylsulfonyl group, and particularly those having excellent heat resistance Become.

Representative examples of the anion represented by the general formula (2c) include, for example, [(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] ⁻ , (C F 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, and the like.

(Anion represented by General Formula (2d))

[In the general formula (2d), R ⁵ represents a halogenated hydrocarbon group which 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) has the same meaning as the halogenated hydrocarbon group in R ¹ of the general formula (2a) described above. The halogenated hydrocarbon group 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, which is particularly excellent in heat resistance.

As a representative example of the anion represented by General formula (2d), the anion shown below can be mentioned, for example.

Z in the general formula (2) ^- as is preferably the anion represented by the general formula (2b) or (2c). Also, specific examples of anions that can be suitably 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 General formula (1) is compoundable using a well-known synthetic | combination method. An example of the synthesis method is described below.
The polymer (A) of the present invention is a solution in which a zwitterion resin, which is a precursor of the polymer (A), is dissolved in water or a water-soluble solvent, and the general formula (2a) to (2d) of the present invention. And an anionic compound having an anion (Z ⁻ ) and a solution in which an anionic compound having an anion (Z ⁻ ) is dissolved in water or a water-soluble solvent are mixed and stirred, and then a cationic dye having a cation (B ⁺ ) of the present invention It can be easily obtained by adding a solution dissolved in water or a water-soluble solvent dropwise and mixing and stirring. In an aqueous solution, the cationic group of the zwitterionic resin and the specific anion (Z ⁻ ) of the anionic compound of the present invention, and the anionic group of the zwitterionic resin and the cation (B ⁺ ) of the cationic dye respectively bind ionically As a result, it becomes insoluble in water and a salt forming compound precipitates. The order of use of the anionic compound and the cationic dye may be reversed, and the amphoteric resin, the anionic compound and the cationic dye may be used alone or in combination of two or more different structures. You may

  When the molar ratio of the cationic group to the anionic compound in the amphoteric resin is in the range of 10/1 to 1/10, the salt forming compound of the present invention is used. The ratio can be suitably adjusted, and is more preferably in the range of 5/1 to 1/5, and further preferably in the range of 2/1 to 1/2. In addition, if the molar ratio of the anionic group to the cationic compound in the amphoteric resin is in the range of 10/1 to 1/10, the salt forming compound of the present invention can be suitably adjusted, and it is 5/1 to 1/5. The range is more preferable, and the range of 2/1 to 1/2 is more preferable.

(Production Method of Amphoteric Ion Resin as Precursor of Polymer (A))
The zwitterionic resin which is a precursor of the polymer (A) can be synthesized using a known synthesis method. The following method (i) (ii) is mentioned as a preferable manufacturing method.
«Production method (i)»
The method of polymerizing the ethylenically unsaturated monomer (b1) which is a precursor of the repeating unit represented by General formula (1), and another ethylenically unsaturated monomer (b3) by well-known polymerization reaction.

«Production method (ii)»
An intermediate polymer (a) obtained by a known polymerization reaction of an ethylenically unsaturated monomer (b2) capable of reacting with a modified species (b4) and another ethylenically unsaturated monomer (b3), A method of reacting modified species (b4).
Each manufacturing method will be described below.

«Production method (i)»
As an ethylenically unsaturated monomer (b1) which is a precursor of the repeating unit represented by General formula (1), the monomer represented by following General formula (4) is mentioned.

(Ethylenically 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 represents a group represented by the general formula (6), Y ^- is, CO ₂ ^- or SO ₃ ^- represents a. ]

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 General Formula (4) has the same meaning as the divalent linking group in R ¹² and R ¹³ of General Formula (1).

The monovalent organic group in R ⁵¹ and R ⁵² in the general formula (5) has the same meaning as 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 in the general formula (6) has the same meaning as the monovalent organic group in R ³¹ and R ³² of the general formula (3).

As a compound represented by General formula (4), the compound shown, for example to the following (4-1 to 4-24) is mentioned.

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

(Other ethylenic unsaturated monomers (b3))
Examples of other ethylenically unsaturated monomers (b3) include acrylic monomers, carboxyl group-containing ethylenically unsaturated monomers, and other monomers.
Examples of acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Alkyl (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate;
Cycloaliphatic such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl oxyethyl (meth 9 acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate Formula alkyl (meth) acrylates;
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate and 3-methyloxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic substituent such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy ethylene oxide modified (meth) acrylate, and paracumyl phenoxy ethylene oxide modified (meth) acrylate;
Methoxypolypropylene glycol (meth) acrylate, and alkoxypolyalkylene glycol (meth) acrylates such as ethoxy polyethylene glycol (meth) acrylate; and
(Meth) acrylamide (In addition, when it describes as "(meth) acrylamide", acrylamide and / or methacrylamide shall be shown. The following is the same.), N, N- dimethyl (meth) acrylamide, N, N -(Meth) acrylamides, such as -diethyl (meth) acrylamide, N- isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloyl morpholine, etc. are mentioned.

  As a carboxyl group-containing ethylenic unsaturated monomer, for example, acrylic acid, methacrylic acid, ε-caparolactone addition acrylic acid, ε-couplerolactone addition methacrylic acid, itaconic acid, maleic acid, fumaric acid, and croton An acid etc. are mentioned.

Other monomers are, 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.

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

«Production method (ii)»
As an ethylenically unsaturated monomer (b2) which can react with modified | denatured species (b4), the monomer etc. which are represented by following General formula (7) are mentioned.

(Ethylenically 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 a group represented by —N (R ⁷³ ) (R ⁷⁴ ), or P (R ⁷⁵ ) (R ⁷⁶ ), or the following general formula (8), and R ^{73 to} R ⁷⁶ each independently represent , 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 for R ⁷² in the general formula (7) has the same meaning as the divalent linking group for R ¹² in the general formula (1).
The monovalent organic group in R ^{73 to} R ⁷⁶ in the general formula (7) has the same meaning as the monovalent organic group in the general formulas (2) and (3).
The monovalent organic group in R ⁸¹ and R ⁸² in the general formula (8) has the same ^{meaning as} 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-tetramethyl piperidyl methacrylate, 1,2,2,6,6-pentamethyl piperidyl 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 (Meth) 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 ethylenic unsaturated monomers (b3))
The other ethylenically unsaturated monomer (b3) is the same as the ethylenically unsaturated monomer (b3) in the production method (i).

(Denatured species (b4))
As the modifying species (b4), it is possible to react with Z in the general formula (7) which is a constituent monomer of the polymerization intermediate polymer (a), and after the reaction, to give a structure of the general formula (1) There is no particular limitation, and examples thereof include a compound represented by the following general formula (9) or a compound represented by the following general formula (10).

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, Q is _CO ^{2 -,} SO ₃ - or PO ₄ ^- represents a. ]

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, fluoroacetic acid, bromoacetic acid, iodoacetic acid, chloropropionic acid, fluoropropionic acid, bromopropionic acid, iodopropionic acid, chlorobutanoic acid, and fluorocarbon acid. Butanoic acid, bromobutanoic acid, iodobutanoic acid chloromethanesulfonic acid, fluoromethylsulfonic acid, bromomethanesulfonic acid, iodomethanesulfonic acid, chloropropanesulfonic acid, fluorinated propanesulfonic acid, bromopropanesulfonic acid, iodopropanesulfonic acid, chloro Butane sulfonic acid, fluorinated butane sulfonic acid, bromobutane sulfonic acid, iodobutane sulfonic acid chloromethanephosphonic acid, fluorinated methylphosphonic acid, bromomethanephosphonic acid, iodomethanephosphonic acid, chloropropanephosphonic acid, fluorinated propane Examples include sulfonic acid, bromopropane phosphonic acid, iodopropane phosphonic acid, chlorobutane phosphonic acid, fluorobutane phosphonic acid, bromobutane phosphonic acid, iodobutane phosphonic acid and the like, with preference given to bromoacetic acid, chloropropionic acid and chloroacetic acid. Among them, chloroacetic acid 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. Among 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 it is preferably a mass average molecular weight of 1,000 to 500,000 measured by gel permeation chromatography (GPC), 3, More preferably, 000 to 15,000.

Moreover, it is preferable that the amphoteric ion resin which is a precursor of the polymer (A) suitable for this invention has the characteristic melt | dissolved in the solvent widely used by the coloring composition for color filters. Thereby, a coating film free from the occurrence of foreign matter can be obtained. In particular, dissolution in propylene glycol monomethyl ether acetate is more preferable.

In the zwitterionic 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 entire structure contained in the polymer (A) When the unit is 100% by mass, the total content of the structural units 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 Preferably, it is 10 to 50% by mass, and more preferably 20 to 40% by mass. When an appropriate amount is contained, the adhesion to the substrate and the various durability of the film are further improved.

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

<Other colorants>
The coloring composition (pigment, dye) other than the said salt-forming compound can be used together in the range which does not impair the effect of this invention, in order to adjust chromaticity, etc. to the coloring composition of this invention.

[Pigment]
The coloring composition for color filters of the present invention can be further added with a pigment and used as a coloring composition for color filters. As the pigment, organic or inorganic pigments may be used alone or in combination of two or more. The pigment is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance, and usually an organic pigment is used. Below, the specific example of the organic pigment which can be used for the coloring composition for color filters is shown by a color index number.

Examples of red coloring compositions for forming a 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, 264, 268, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, Red pigments such as 286 or 287 can be used. In addition, red coloring compositions include C.I. I. Orange pigments such as C.I. pigment orange 36, 38, 43, 51, 55, 59, 61, 71, or 73; I. Pigments yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 32, 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, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 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, 1 Yellow pigments such as 6, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or 231 can be used in combination .

Examples of green coloring compositions for forming green filter segments include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63, etc. Green pigments can be used. Moreover, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, patent 4893859 grade | etc., Can also be used. Further, for the green coloring composition, C.I. I. Pigments 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, 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, 181, 181, 181, 181, Yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 199, 213, 214, 218, 219, 220, 221 or 231 can be used in combination.

As a blue coloring composition for forming a blue filter segment, for example, C.I. I. Pigment blue 1, 1: 2, 1: 3, 2, 2: 2, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: Blue pigment 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. It can be used. In the blue colored composition, C.I. I. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination. Moreover, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, patent 4893859 grade | etc., Can also be used.

Examples of cyan coloring compositions for forming cyan filter segments include C.I. I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 etc. Blue pigments may be used alone or in combination.

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

Moreover, as an inorganic pigment, titanium oxide, barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber , Synthetic iron black and the like. The inorganic pigment is used in combination with an organic pigment in order to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between chroma and lightness.

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

<Finening of pigment>
When the coloring agent used for the coloring composition for color filters of this invention is a pigment, it is preferable to refine | miniaturize and use it from a viewpoint of contrast. The method of refining is not particularly limited, and examples thereof include wet grinding, dry grinding, solution precipitation method and the like. Among these, the salt milling process by the kneader method which is 1 type of wet grinding is preferable. 5-90 nm is preferable and, as for the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment, 10-70 nm is more preferable. When the particle diameter is appropriate, the dispersibility is improved and the contrast ratio is further improved.

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

  Examples of water-soluble inorganic salts include sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like. Among these, inexpensive sodium chloride (salt) is preferable. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, with respect to 100 parts by mass of the pigment, in terms of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is easily evaporated, 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. It is preferable to use 5-1000 mass parts with respect to 100 mass parts of pigments, and, as for a water-soluble organic solvent, 50-500 mass parts is more preferable.

  When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin to be 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, preferably water insoluble, and more preferably partially soluble in the organic solvent. As for the usage-amount of resin, 5-200 mass parts is preferable with respect to 100 mass parts of pigments.

<Dye derivative>
The coloring composition for color filters of the present invention can contain any of various dye derivatives known in the prior art. Examples of dye derivatives include organic pigments, anthraquinones, acridones or triazines, compounds having a basic substituent, an acid substituent, or a phthalimidomethyl group which may have a substituent, for example, 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A 2001-335717, JP-A 2003- 128669, JP-A 2003-167112, JP-A 2004-091497, JP-A 2004-307854, JP-A 2007-156395, JP-A 2008-094873, JP-A 2008-094986 Publication No. 2008-095007 Publication No. 2008-19591 JP, but it is not limited to be used those described in Japanese Patent No. 4585781 Patent Publication. The pigment derivative may be added at the time of pigmentation such as salt milling, or may be added at the time of dispersion.

<Binder resin>
The binder resin is a compound necessary for film formation. The binder resin may, for example, be a thermoplastic resin, a thermosetting resin, or an active energy ray-curable resin having an ethylenically unsaturated double bond. Moreover, it is also preferable that active energy ray curable resin has thermosetting. The binder resin is preferably an alkali-soluble resin from the viewpoint of developability.

  20-400 mass parts is preferable with respect to 100 mass parts of coloring agents, and, as for content of the binder resin in the coloring composition of this invention, 50-250 mass parts is more preferable. When an appropriate amount is contained, film formation becomes easy and good color characteristics are easily obtained.

As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric 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 range of 400 to 700 nm in the visible light range.

  The alkali-soluble resin is a resin having an acidic group such as a carboxyl group or a sulfone group. The alkali-soluble resin is, for example, an acrylic resin having an acid group, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or isobutylene / (Anhydride) maleic acid copolymer etc. are mentioned. Among these, the acrylic resin which has an acidic group which heat resistance and transparency improve more, and a styrene / styrene sulfonic acid copolymer are preferable, and the acrylic resin which has 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 an alkali-soluble resin. Thereby, the film after curing has a further improved solvent resistance.

As active energy ray curable resin which has an ethylenically unsaturated double bond, resin which introduce | transduced the unsaturated ethylenic double bond by the method of (a)-and (c) shown below, for example is mentioned.

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers And the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added, 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 unsaturated ethylenic monomers having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxy butyl (meth) acrylate, And 3,4 epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of the reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group. Moreover, unsaturated ethylenic double bond can be further increased by using ethahydrophthalic anhydride or maleic anhydride having unsaturated ethylenic double bond as polybasic acid anhydride.

[Method (b)]
As a similar method of method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.
In this method, more hydroxyl groups derived from the unsaturated ethylenic monomer having an epoxy group are generated as compared with the method (a). When the resin having a cationic group in the side chain, which is used when obtaining the salt forming compound of the present invention, contains oxetanyl group or t-butyl group as a thermally crosslinkable functional group, the method is used as a binder resin ( Use of the resin obtained by b) is preferable because it exhibits higher heat resistance.

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

As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol There may be mentioned hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Also, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid or the like is added can also be used. From the viewpoint of coating foreign matter suppression, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate and the like, but are not limited thereto. Alternatively, two or more types can be used in combination.

The mass average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

When using binder resin as a photosensitive composition, it is preferable to use resin of an acid value of 20-300 mgKOH / g from a dispersibility of a pigment and a salt-forming compound, permeability, developability, and a heat resistance viewpoint. If the acid value is less than 20 mg KOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mg KOH / g, fine patterns may not be left.

The binder resin is preferably used in an amount of 30% by mass or more based on the total mass of the coloring agent (100 mass%) because the film forming property and the various resistances are good, and the coloring agent concentration is high and good. It is preferable to use it in an amount of 500% by mass or less because it can exhibit color characteristics.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further included in combination with the thermoplastic resin which is a binder resin. As a thermosetting compound, for example, an epoxy compound and / or resin, an oxetane compound and / or resin, a benzoguanamine compound and / or resin, a rosin modified maleic acid compound and / or resin, a rosin modified fumaric acid compound and / or resin, Examples thereof 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 adjust the viscosity of the coloring composition appropriately.

  As an organic solvent, for example, 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-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, 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 monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether Chill 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters.

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

A coloring agent can be used individually or in combination of 2 or more types.

  In addition, the organic solvent is used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the coloring agent because it can adjust the coloring composition to an appropriate viscosity and form a colored film having an intended uniform film thickness. Is preferred.

<Photopolymerizable monomer>
The coloring composition of the present invention may further be added with a photopolymerizable monomer and / or a photopolymerization initiator and used as a photosensitive coloring composition for a color filter. The photopolymerizable monomer which may be added to the coloring composition of the present invention includes a monomer or an oligomer which is cured by ultraviolet light, heat or the like to form a transparent resin.

  Examples of monomers and oligomers that cure by ultraviolet light and heat to form a transparent resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglyci Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Various acrylic and methacrylic esters such as (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy ester Examples include, but not limited to, chill (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

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

  5-400 mass parts are preferable with respect to 100 mass parts of coloring agents, and, as for the compounding quantity of a photopolymerizable monomer, 10-300 mass parts is more preferable. When incorporated in an appropriate amount, photocurability and developability are further improved.

<Photoinitiator>
The coloring composition for color filters of the present invention can contain a photopolymerization initiator. Thereby, when forming a filter segment by the photolithographic method, photocuring becomes easy. 5-200 mass% is preferable with respect to 100 mass parts of coloring agents, and, as for the compounding quantity of a photoinitiator, 10-150 mass% is more preferable. When incorporated in an appropriate amount, photocurability and developability are further improved.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, also Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4'-methoxystyryl) -6-triazine; 1- (N-4-benzoylphenyl-carbazol-3-yl) -butane-1,2-dione 2-oxime-O-acetate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) Ethylidene) An oxime ester compound such as hydroxylamine; A phosphine compound such as bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide or 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide; 9, 10-phenanth Quinone compounds such as lenquinone, camphorquinone, ethyl anthraquinone; borate compounds; carbazole System compounds; imidazole compounds; or titanocene compounds are used.

A photoinitiator can be used individually or in combination of 2 or more types.

5-200 mass% is preferable with respect to 100 mass parts of coloring agents, and, as for the usage-amount to a photoinitiator, 10-150 mass% is more preferable. When used in an appropriate amount, photocurability and developability are further improved.

<Sensitizer>
The coloring composition can use a photoinitiator and a sensitizer together.
Examples of sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinones. Derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives Tetrapyrazinoporphyrazine derivative, Phthalocyanine derivative, Tetraazaporphyrazine derivative, Tetraquinoxaliloporphyrazine derivative, Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrilium derivative, Tetraphyrin derivative, Annulene derivative, Spiropyran derivative, Spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acyl phosphine oxide, methylphenylglyoxylate, benzyl, 9, 10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno Examples include enone, 4,4'-diethylaminobenzophenone and the like.

In addition, Ogawara Shin et al., "Dye Handbook" (1986, Kodansha), Ogawara Shin et al., "Chemicals of functional dyes" (1981, CMC), Ikemori Tadazami et al., "Special functional materials" (1986, And sensitizers described in CMC).

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

3-60 mass% is preferable with respect to 100 mass parts of photoinitiators, and, as for the usage-amount of a sensitizer, 5-50 mass% is more preferable. When used in an appropriate amount, photocurability and developability are further improved.

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

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, Examples thereof include 2-ethylhexyl 4-dimethylaminobenzoate and N, N-dimethyl paratoluidine.

<Leveling agent>
The coloring composition can contain a leveling agent. Thereby, the coatability is further improved, and the surface smoothness of the film is further improved.
The leveling agent is, for example, in addition to dimethylsiloxane, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants (surfactants, anionic surfactants, etc. It can be mentioned.
The dimethylsiloxane is preferably a dimethylsiloxane having a polyether structure and / or a polyester structure in the main chain. Commercial 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, BIC Chemie, manufactured by Toray Dow Corning. Company-made BYK-333 etc. are mentioned. Commercially available dimethylsiloxanes having a polyester structure in the main chain include BYK-310, BYK-370 and the like manufactured by Big Chemie.

Anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, Examples thereof include triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Cationic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

The leveling agents 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.

  As an epoxy compound, for example, 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, biphenol Type epoxy resin, bisphenol-A novolac type epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and the like.

  Commercial products of the phenol novolac epoxy resin are, for example, Epiclon N-740, Epiclon N-770, Epiclon N-775, manufactured by DIC, D.C. E. N438, RE-306 manufactured by Nippon Kayaku Co., Ltd., jER152 manufactured by Mitsubishi Chemical Corporation, jER154 and the like.

  Commercial products of cresol novolac type epoxy resin are Epiclon N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-680, Epiclon N-695, Epiclon N-665-EXP, manufactured by DIC. Epiclon N-672-EXP, Nippon Kayaku Co., Ltd. EOCN-102S, EOCN-103S, EOCN-104S, Union Carbide Co., Ltd. UVR-6650, Sumitomo Chemical Co., Ltd. ESCN-195 etc. are mentioned.

  Commercially available products of trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H manufactured by Nippon Kayaku Co., Ltd., TACTIX-742 manufactured by Dow Chemical Co., jER E1032H60 manufactured by Mitsubishi Chemical Co., and the like.

  Commercially available products of dicyclopentadiene phenol type epoxy resin include Epiclon EXA-7200 manufactured by DIC, TACTIX-556 manufactured by Dow Chemical Co., and the like.

  Commercially available products of bisphenol type epoxy resin are jER 828 and jER 1001 manufactured by Mitsubishi Chemical Corp., UVR-6410 manufactured by Union Carbide Corp., and D.D. E. Bisphenol-A type epoxy resin such as R-331, YD-8125 manufactured by Nippon Steel Epoxy Co., Ltd., and bisphenol-F type epoxy resin such as YDF-8170 manufactured by Nippon Carbide Epoxy Co., Ltd. Can be mentioned.

  Commercial products of biphenol type epoxy resins include biphenol type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and bixylenol type epoxy resins such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation. It can be mentioned.

  Commercially available products of the bisphenol A novolac epoxy resin include Epiclon N-880 manufactured by DIC, jER E157S75 manufactured by Mitsubishi Chemical Corporation, and the like.

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

  Commercially available products of the alicyclic epoxy resin include Sekicide 2021 P, 2081 and 2000 manufactured by Daicel Co., Ltd., and EPOID PB 3600, PB 4700, GT 401, EHPE-3150, and Cyclomer M100.

  Commercially available heterocyclic epoxy resins include TEPIC-L, TEPIC-H, TEPIC-S, etc. manufactured by Nissan Chemical Industries, Ltd.

An epoxy compound can be used individually or in combination of 2 or more types.

  0.5-50 mass% is preferable in 100 mass% of non volatile matters of a coloring composition, and, as for content of an epoxy compound, 1-40 mass% is more preferable. The heat resistance is further improved by containing an appropriate amount.

<Oxetane Compound>
The coloring composition can contain an oxetane compound. The oxetane compounds include compounds having a monofunctional, bifunctional, and trifunctional or higher functional oxetane group.

  Compounds having a monofunctional oxetane group are, for example, (3-ethyl oxetan-3-yl) methyl acrylate, (3-ethyl oxetan-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 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 can be mentioned. Examples of commercially available products include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101 and 212 manufactured by OXE-30 Toagosei Co., Ltd.

  The compound having a bifunctional oxetane group is, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 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)] Methylether-3-ethyl-3-hydroxymethyl oxetane, 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] ethane, 1,3-bis [( -Ethyl-3-oxetanylmethoxy) methyl] propane, ethyleneglycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3- (3-ethyl-3-oxetanylmethyl) ether Ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3- (3-ethyl-3-oxetanylmethyl) ether 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 And EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether and the like. Examples of commercially available products include Ube Industries, Ltd., OXBP, OXTP, and Toagosei Co., Ltd., OXT-121, OXT-221, and the like.

  Examples of compounds having a trifunctional or higher oxetane group include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl). -3-oxetanyl methyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa (3- Ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ether Radical polymerization of (meth) acrylic monomers such as leu-3-oxetanylmethyl) ether, a resin containing an oxetane group (for example, an oxetane-modified phenolic novolac resin described in Japanese Patent No. 3783462, etc.) and the above-mentioned OXE-30 The polymer obtained is mentioned.

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

  0.5-50 mass% is preferable in 100 mass% of non volatile matters of a coloring composition, and, as for content of an oxetane compound, 1-40 mass% is more preferable. The heat resistance is further improved by containing an appropriate amount.

<Hardening agent, hardening 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 compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Among these, a compound having two or more phenolic hydroxyl groups in one molecule, and an amine-based curing agent are preferable.
The curing accelerator is, for example, an amine compound (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N , N-dimethylbenzylamine etc., quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg, dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-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-methacryloyloxyethyl) -S-Triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl- S-triazine, an isocyanuric acid adduct etc. etc. are mentioned.

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

  As for the usage-amount of a hardening agent and a hardening accelerator, 0.01-15 mass% is preferable with respect to 100 mass parts of thermosetting resins, respectively.

<UV absorber>
The coloring composition can 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 in 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 light absorber is preferably 1 to 20% by mass in 100% by mass of the non-volatile matter of the photosensitive coloring composition. When the total content of the photopolymerization initiator and the ultraviolet light absorber is less than the above, the adhesion is weakened to cause peeling of the pixel. When the total content 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, octyl-3 [3-tert -Butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro) -2H-benzotriazol-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl) 2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- ( 2H-benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, compound of C7-9 side chain and linear alkyl esters, 2- (2H-benzotriazol-2-yl) -4 , 6-Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3) , 3- tetramethylbutyl) phenol.

Commercial products are BASF "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, and the like.

The triazine organic compounds are, for example, 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazin-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-glycidic ester, 2,4-bis "2-hydroxy-4-butoxyphenyl -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like.

Commercial products are "KEMISORB 102" manufactured by Chemi-Pro Chemical, "TINUVIN 400" manufactured by BASF, "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", "TINUVIN 1577", ADEKA "Adekastab LA-46", "Adekastab LA-F70", "CYASORB UV-1164" manufactured by Sun Chemical Co., Ltd., and the like.

The benzophenone series organic compounds are, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n -Octoxybenzophenone, 2,2-di-hydroxy-4-methoxybenzophenone and the like.

Commercially available products are “KEMISORB 10”, “KEMISORB 11”, “KEMISORB 11S”, “KEMISORB 12”, “KEMISORB 111” manufactured by Chemi-Pro Chemical Co., “SEESORB 101”, “SEESORB 107” manufactured by Shipro Kasei Co., Ltd. "Adeka stub 1413" etc. are mentioned.

<Thiol chain transfer agent>
The coloring composition can contain a thiol chain transfer agent. When a thiol 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 a thiyl radical which is less susceptible to inhibition of polymerization by oxygen, thereby improving the photosensitivity. Thereby, the photocurability from the coating surface to the deep part of the coating is further improved.

Examples of multifunctional thiols include hexanedithiol, decanedithiol, 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, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutyla) Mino) -4,6-dimercapto-s-triazine and the like can be mentioned, and preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents 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%, and more preferably 2 to 8%, in 100% by mass of the nonvolatile matter of the coloring composition. When used in an appropriate amount, the photosensitivity is improved and a coating of a good shape is obtained.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. An antioxidant can suppress that the film formed from a coloring composition oxidizes and yellows by heating processes, such as thermosetting, and can maintain the transmittance | permeability of a film. In particular, when the coloring agent concentration of the photosensitive coloring composition is high, the crosslinking component decreases relatively, and the yellowing of the heat process occurs when the use of a highly sensitive crosslinking component or the increase of the photopolymerization initiator is taken. It is to become stronger. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation in the heating step and to obtain a high transmittance of the coating film.

  The "antioxidant" in the present invention may be a compound having an ultraviolet light absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, a hindered phenol type or hindered amine type as an antioxidant. Examples thereof include phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used. Further, the antioxidant used in the present invention is preferably one containing no halogen atom.

  Among these antioxidants, preferred are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants from the viewpoint of achieving both the transmittance and sensitivity of the coating film. Agents.

Examples of hindered phenolic antioxidants include 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) -Tert-Butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-4 Nonylphenol, 2,2'-Isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-Butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- S- (6-t-Butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis- (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-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydro) And the like. Other compounds of oligomer type and polymer type having a hindered phenol structure can also be used.
Commercial products are Adekastab AO-20, AO-30, AO-40, AO50, AO60, AO320 manufactured by ADEKA, KEMINOX 101, 179, 76, 9425 manufactured by Chemipro, IRGANOX 1010, 1035, 1076, 1098, 1135 manufactured by BASF. 1330, 1726, 1425 WL, 1520 L, 245, 259, 3114, 5057, 565, and sianox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd., and the like.

As the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butane tetracarboxylate, 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-triazine-2,4-diyl) {(2, 2,6,6-Tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-Pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomeric types having a hindered amine structure And the A primer type compound etc. can also be used.
Commercially available products are Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-87 manufactured by Adeka. 402F, LA-502XP, KAMISTAB 29, 62, 77, 29, 94, manufactured by Chemi-Pro Chemical, Tinuvin 249, TINUVIN 111 FDL, 123, 144, 292, 5100, manufactured by BASF, Ciasorb UV-3346, manufactured by Sun Chemical Co., UV- 3529, UV- 3853 grade | etc., Is mentioned.

As a phosphorus antioxidant, tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 'isopropylidene diphenol alkyl phosphite, tris nonyl phenyl phosphite, tris dinonyl phenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidene bis (3-methyl-) 6-t-Butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxy phosphonyloxy)-Ben Zen, ethyl phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.
Commercially available products include Adekastab PEP-36, PEP-8, HP-10, Adekastab 2112, 1178, 1500, C, 3013, TPP manufactured by ADEKA, IRGAFOS 168 manufactured by BASF, Hostanox P-EPQ manufactured by Clariant Chemicals, and the like.

As a sulfur-based antioxidant, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 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.
Commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by Chemi-Pro Chemical.

As the benzotriazole-based antioxidant, compounds of oligomer type and polymer type having a benzotriazole structure can be used.
Commercially available products are Adekastab LA-29, LA-31 RG, LA-32, LA-36, -412S manufactured by ADEKA, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemi-Pro Chemical, TINUVIN PS, 99-2 manufactured by BASF. , 384-2, 900, 928, 1130 and the like.

Examples of benzophenone antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4. -Octadecyloxy benzophenone, 2,2 'dihydroxy-4-methoxy benzophenone, 2,2'dihydroxy-4,4'-dimethoxy benzophenone, 2,2 ', 4,4'- tetrahydroxy benzophenone, 2-hydroxy-4 -Methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.
Examples of commercially available products include Adekastab 1413 manufactured by ADEKA, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemi-Pro Chemical, UV-12, UV-329 manufactured by Sun Chemical Co., and the like.

As a triazine type antioxidant, a 2, 4- bis (allyl) 6- (2-hydroxyphenyl) 1, 3, 5- triazine etc. are mentioned. In addition, oligomer type and polymer type compounds having a triazine structure can also be used.
Commercially available products include Adekastab LA-46 and F70 manufactured by ADEKA, KEMISORB 102 manufactured by Chemi-Pro Chemical, TINUVIN 400, 405, 460, 477 and 479 manufactured by BASF, and Ciasorb UV-1164 manufactured by Sun Chemical Co., Ltd.

  Examples of the salicylate-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate and the like. In addition, oligomer type and polymer type compounds having a salicylate structure can also be used.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 100% by mass of the nonvolatile matter of the coloring composition, because the spectral characteristics and the sensitivity are good.

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

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyrocatechol, tetraethyl phosphine, tetraphenyl phosphine, etc. Organic phosphine, phosphite and the like can be mentioned. The use amount of the storage stabilizer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

Adhesion improvers include vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,3, 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-aminopropyl trie Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. 0.01-10 mass parts is preferable with respect to 100 mass parts of coloring agents, and, as for the usage-amount of a close_contact | adherence improvement agent, 0.05-5 mass% is more preferable.

<Method of producing coloring composition>
The coloring composition of the present invention comprises a dye containing a polymer (A) containing a repeating unit represented by the general formula (1), a binder resin, and a mixture containing an organic solvent, for example, a three-roll mill, It is preferable to finely disperse and manufacture using various dispersion means such as roll mill, sand mill, kneader or attritor. In addition, when a plurality of colorants are used, the coloring composition of the present invention can also be produced by separately preparing dispersions and then mixing these dispersants. When the solubility of the coloring agent such as dye is high, specifically, the solubility in the solvent used is high, and if it is in a state where it is not dissolved by stirring and no foreign matter is confirmed, the finely dispersing step as described above is performed. It does not have to be. When the mixture contains a pigment, it is preferable to use a dispersing aid such as a dye derivative in combination.

Moreover, when using a coloring composition as a resist material, it is preferable to prepare as a solvent development type or alkali development type coloring composition. The solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, another dispersion aid, and an additive. 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 the coloring agent is dispersed in the coloring composition, a dye derivative, a dispersing agent (for example, a resin type dispersing agent), a dispersing aid (for example, a surfactant) and the like can be appropriately used. The dispersion assistant is excellent in the dispersion of the colorant and has a large effect of preventing the reaggregation of the colorant after the dispersion, so that a color filter having a high spectral transmittance can be obtained. The dye derivative is as described above.

<Dispersing agent>
(Resin type dispersant)
The resin type dispersant has a colorant affinity site having a property of adsorbing to a colorant, and a site compatible with components other than the colorant. The resin type dispersant includes, for example, polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, poly Siloxane, long chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amide formed by reaction of poly (lower alkylenimine) with polyester having free carboxyl group, salts thereof and the like Water-soluble agents such as oil-based dispersants, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water soluble polymer, polyester, modified polyacry Over preparative system, an ethylene oxide / propylene oxide adduct, phosphoric acid ester, and the like.

As the dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, and a nitrogen atom-containing graft copolymer, a tertiary amino group in a side chain, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing

  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 BIC Chem. Japan. 167, 168, 170, 171, 174, 180, 181, 182, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2095, 2150, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al., Japan Lubris SOLSPERSE-3000, 9000, 3000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 20000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32500, 32500, 34750, 35100, 36600, 38500, 41000, 41090, 41090, 41090 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 458, 4008, 4009, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 , 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 453, 454, 4550, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

Moreover, as a resin type dispersing agent used by this invention, it is also preferable to contain following (S1) or (S2) as a resin type dispersing agent which has 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 Resin type dispersant which is united.

[Resin type dispersant (S1)]
The resin type dispersant (S1) can be produced by a known method such as WO 2008/007776, JP 2008-029901, JP 2009-155406 and the like. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at an end, and 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. Among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used because the terminal hydroxyl group is preferably plural.

That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, has 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. 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 anhydride ring is opened to form a carboxylic acid. Produces

[Resin type dispersant (S2)]
The resin type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, etc. 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. Among them, in the presence of the reaction product of the hydroxyl group of 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 Preferably, it is a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1).

(S1) and (S2) are differences in whether the introduction of the polymer portion obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. Although molecular weight etc. may differ somewhat depending on various conditions, if the raw material and the reaction conditions are the same, theoretically the same one can be obtained.

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

5-200 mass parts is preferable with respect to 100 mass parts of coloring agents, and, as for the usage-amount of a dispersing agent, 10-100 mass parts is more preferable. The film formability is further improved by using an appropriate amount.

<Dispersion aid>
(Surfactant)
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more, but it is not necessarily limited thereto.

Dispersion aids can be used alone or in combination of two or more.

  0.1-55 mass parts is preferable with respect to 100 mass parts of coloring agents, and, as for the usage-amount of a dispersion adjuvant, 0.1-45 mass parts is more preferable. Dispersibility improves more when used in an appropriate amount.

<Removal of coarse particles>
The coloring composition of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, filtration with a sintered filter or membrane filter, and the like. It is preferable to carry out the removal of the mixed dust. Thus, the coloring composition preferably contains substantially no particles 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 comprises a substrate and a red filter segment, a green filter segment, and a blue filter segment. Also, the color filter may 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 the red filter segment, the green filter segment, and the yellow filter segment is preferably formed using the coloring composition of the present invention, to form a green filter segment More preferable.

<Method of manufacturing color filter>
Although a color filter can be produced by a printing method, a photolithography method or the like, a photolithography method is preferable.

  The formation of the filter segment is preferably a photolithographic method. The photolithography method uses, for example, a coating method such as spray coating, spin coating, slit coating, or roll coating on a transparent substrate of a photosensitive coloring composition prepared as a solvent developing type or alkali developing type coloring resist. And coated so that the dry film thickness is 0.2 to 10 μm. The coating is exposed to ultraviolet radiation through a mask having a predetermined pattern.

Thereafter, it is immersed in a solvent or an alkaline developer, or the developer is sprayed by a spray or the like to remove an uncured portion and form a desired pattern to form a filter segment and a black matrix. Furthermore, it can be heated as needed to promote the polymerization of the filter segment and black matrix formed by development. The photolithography method can form a filter segment with high accuracy as compared to the printing method.

For the development, for example, an aqueous solution such as sodium carbonate and sodium hydroxide as an alkali developing solution; an organic alkali such as dimethylbenzylamine, triethanolamine and tetramethylammonium hydroxide can be mentioned. Moreover, a developing solution can use an antifoamer and surfactant. Examples of the development processing method include a shower development method, a spray development method, a dip (immersion) development method, and a paddle (liquid accumulation) development method.

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

Examples of the substrate include glass plates such as soda lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc .; and resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate. Further, on the surface of the substrate, it is preferable to provide a transparent electrode formed of indium oxide, tin oxide or the like for driving liquid crystal after panelization. When the color filter is used for a solid-state imaging device, the substrate is preferably a silicon wafer. The substrate includes a transmissive substrate and a reflective substrate depending on the application.

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

0.2-10 micrometers is preferable and, as for the film thickness of a filter segment, 0.2-5 micrometers is more preferable. At the time of coating, a drying process can be performed. Examples of the drying apparatus include a vacuum dryer, a convection oven, an IR oven, a hot plate and the like.

If the black matrix is formed in advance before forming the filter segments on the substrate, the contrast of the display panel can be further enhanced. The black matrix may be, 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, but is not limited thereto. Alternatively, thin film transistors (TFTs) may be formed in advance on the transparent substrate or the reflective substrate, and then filter segments may be formed. By forming the filter segments on the TFT substrate, the aperture ratio of the panel can be increased and the luminance can be improved.
An overcoat film or a transparent conductive film can be formed on the color filter as needed.

The color filter of the present invention is bonded to the opposite substrate using a sealing agent, and after injecting liquid crystal from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or retardation film is used as a substrate if necessary. The color liquid crystal display device is manufactured by bonding to the outer side of. This color liquid crystal display device can be twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), critically aligned (VA), optically convensend bend (OCB) Etc.) can be used in a liquid crystal display mode in which coloring is performed.

  The color filter of the present invention can also be used for producing a color imaging device, an organic EL display device, an electronic paper, etc. in addition to the color liquid crystal display device.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereby. In addition, unless there is particular notice, "part" means "mass part" and "%" means "mass%."

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by direct measurement of the primary particle size from an electron micrograph using a transmission (TEM) 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 diameter of the primary pigment particles. Next, with respect to 100 or more pigment particles, the volume (mass) of each particle is determined by approximating to the cube of the determined particle diameter, and the volume average particle diameter is defined as the average primary particle diameter.

(Mass average molecular weight of binder resin and dispersant)
The mass average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation) using polystyrene as the developing solvent and polystyrene conversion It is a mass mean molecular weight (Mw).

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

(Molecular weight of polymer A and intermediate polymer (a))
The number average molecular weight (Mn) and the mass average molecular weight (Mw) of the polymer A were measured using HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, using SUPER-AW 3000 as a column, and using 30 mM triethylamine and 10 mM LiBr as an eluent. It is the number average molecular weight (Mn) and mass mean molecular weight (Mw) of polystyrene conversion measured using the N, N- dimethylformamide solution.

(Amine Value of Polymer A and Intermediate Polymer (a))
The amine value of the basic resin type dispersant is a value obtained by converting the total amine value (mg KOH / g) measured in accordance with the method of ASTM D 2074 into non-volatile components.

<Production of binder resin solution>
(Binder resin solution 1)
70.0 parts of methoxypropyl acetate is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer are attached to a separable four-neck flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Alonix M110" manufactured by Toagosei Co., Ltd.) from a dropping pipe A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, approximately 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and methoxypropyl acetate is added to the resin solution synthesized above so that the non-volatile content is 40%. The binder resin solution 1 was prepared.

(Binder resin solution 2)
Into a separable 4-neck flask equipped with a thermometer, a condenser, a nitrogen gas inlet pipe, a dropping pipe, and a stirrer, charge 370 parts of methoxypropyl acetate, raise the temperature to 80 ° C, replace the inside of the flask with nitrogen, and then from the dropping pipe 18 parts of paracumyl phenol ethylene oxide modified acrylate (ALONIX M110 manufactured by TOAGOSEI CO., LTD.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-azobisisobutyro nitrile 2 .0 part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was allowed to react at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100 ° C. for 1 hour. Next, the inside of the vessel is replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl group), 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are charged into the vessel, and the temperature is raised to 120 ° C. The reaction was continued for 6 hours, and when the acid value of non-volatile portion reached 0.5, the reaction was completed to obtain a copolymer solution. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a resin solution. After cooling to room temperature, approximately 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and methoxypropyl acetate is added to the resin solution synthesized above so that the non-volatile content is 40%. The binder resin solution 2 was prepared. The mass average molecular weight (Mw) was 19,000.

<Production of finely divided pigment>
(Red finely divided pigment (P-1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of CI pigment red 254 ("IRGAZINRED 2030" manufactured by BASF Japan Ltd.), 1400 parts of crushed sodium chloride 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. The mixture is poured into 8000 parts of hot water and stirred for about 2 hours with a high speed mixer while heating to about 70 ° C. to form a slurry, and filtration and washing with water are repeated to remove salt and solvent, and then 24 hours at 85 ° C. Drying gave 190 parts of a finely divided red pigment (P-1). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Red finely divided pigment (P-2))
Red pigment C.I. I. 200 parts of pigment red 177, 1400 parts of crushed common salt, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 5 hours. The mixture is poured into 8000 parts of hot water and stirred for about 2 hours with a high speed mixer while heating to about 70 ° C. to form a slurry, and filtration and washing with water are repeated to remove salt and solvent, and then 24 hours at 85 ° C. Drying gave 190 parts of a finely divided red pigment (P-2). The average primary particle diameter of the obtained pigment was 23.5 nm.

(Red finely divided pigment (P-3))
200 parts of the red pigment 1 of the formula (5), 1400 parts of crushed sodium chloride 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. The mixture is poured into 8000 parts of hot water and stirred for 2 hours with a high speed mixer while heating to about 70 ° C. to form a slurry, repeated filtration, washing with water to remove salt and solvent, and drying at 80 ° C. for 24 hours 190 parts of a finely divided red pigment (P-3) were obtained. The average primary particle diameter of the obtained pigment was 29.3 nm.

Formula (5)

(Blue finely divided pigment (P-4))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.) 100 parts, crushed salt 800 parts, and diethylene glycol 100 parts are charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 12 hours did. The mixture is poured into 3000 parts of hot water and stirred for about 1 hour with a high speed mixer while heating to about 70 ° C. to form a slurry, and after repeated filtration and washing with water to remove salt and solvent, it is kept at 80 ° C. for 24 hours. Drying gave 98 parts of a blue finely divided pigment (P-4). The average primary particle diameter of the obtained pigment was 28.3 nm.

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

Formula (7)

120 parts of the quinophthalone yellow pigment represented by the formula (7) obtained above, 1600 parts of crushed sodium chloride and 100 parts of diethylene glycol are charged in a stainless steel 1 gallon kneader (made by Inoue Seisakusho) and kneaded at 70 ° C. for 18 hours did. The mixture is poured into 5000 parts of hot water and stirred for about 1 hour with a high speed mixer while heating to about 70 ° C. to form a slurry, filtering and washing with water repeatedly to remove salt and solvent, and then 24 hours at 80 ° C. Drying gave 118 parts of a quinophthalone-based yellow finely divided pigment (P-5). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Yellow micronized pigment (P-6))
Yellow pigment C.I. I. 200 parts of C.I. Pigment Yellow 150, 1400 parts of crushed sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 6 hours. The mixture is poured into 8000 parts of hot water and stirred for 2 hours with a high speed mixer while heating to about 70 ° C. to form a slurry, repeated filtration, washing with water to remove salt and solvent, and drying at 80 ° C. for 24 hours 190 parts of a yellow finely divided pigment (P-6) was obtained. The average primary particle diameter of the obtained pigment was 28.5 nm.

(Yellow micronized pigment (P-7))
Yellow pigment C.I. I. 200 parts of C.I. pigment yellow 138, 1400 parts of crushed sodium chloride and 360 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 6 hours. The mixture is poured into 8000 parts of hot water and stirred for 2 hours with a high speed mixer while heating to about 70 ° C. to form a slurry, repeated filtration, washing with water to remove salt and solvent, and drying at 80 ° C. for 24 hours 190 parts of a yellow finely divided pigment (P-7) were obtained. The average primary particle size of the obtained pigment was 27.1 nm.

(Yellow micronized pigment (P-8))
Yellow pigment C.I. I. 200 parts of C.I. pigment yellow 139, 1400 parts of crushed sodium chloride and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 6 hours. The mixture is poured into 8000 parts of hot water and stirred for 2 hours with a high speed mixer while heating to about 70 ° C. to form a slurry, repeated filtration, washing with water to remove salt and solvent, and drying at 80 ° C. for 24 hours To give 190 parts of a yellow finely divided pigment (P-8). The average primary particle size of the obtained pigment was 25.4 nm.

(Purple micronized pigment (P-9))
Dioxazine purple pigment C.I. I. 120 parts of pigment violet 23 ("Fast Violet RL" manufactured by Clariant), 1600 parts of crushed sodium chloride, 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. The mixture is poured into 5000 parts of hot water and stirred for about 1 hour with a high speed mixer while heating to about 70 ° C. to form a slurry, filtering and washing with water repeatedly to remove salt and solvent, and then 24 hours at 80 ° C. Drying gave 118 parts of a purple finely divided pigment (P-9). The average primary particle diameter of the obtained pigment was 26.4 nm.

<Manufacture of dispersant>
(Dispersant solution 1)
70 parts of methyl methacrylate, 20 parts of t-butyl methacrylate, and 10 parts of methacrylic acid were charged into a reaction vessel equipped with a gas introduction pipe, a thermometer, a condenser and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 6.0 parts of 1-thioglycerol was added to react for 12 hours. It was confirmed by the measurement of non-volatile components 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 allowed to react at 100.degree. C. for 7 hours. The acid value of 98% or more of the acid anhydride was confirmed to be half-esterified by the measurement of acid value, and the reaction was terminated, and the non-volatile content was 50%. I got

(Dispersant solution 2)
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 25 parts of (3-ethyloxetan-3-yl) methyl methacrylate acrylate, 45 parts of t-butyl methacrylate, 20 parts of methyl methacrylate, and 10 parts of methacrylic acid Charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and 6.0 parts of 1-thioglycerol was added to react for 12 hours. It was confirmed by the measurement of non-volatile components 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 allowed to react at 100.degree. C. for 7 hours. The acid value of 98% or more of the acid anhydride is confirmed to be half-esterified, and the reaction is terminated. The dispersant solution 2 with 50% non-volatile content, 101 mg KOH / g acid value and 9,000 weight average molecular weight I got

(Dispersant solution 3)
BASF "EFKA 4300" was adjusted with propylene glycol monomethyl ether acetate so as to have a non-volatile content of 50%. This was named Dispersant Solution 3.

<Production of Polymer (Amphatic Ion Resin) Having Betaine Structure in Side Chain>
(Polymer J-1)
100 parts of isopropyl alcohol is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen. Parts, 15 parts of N, N-dimethylaminoethyl methacrylate, 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 polymerization was carried out for 2 hours while maintaining this temperature. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of polymer intermediate (j-1). Subsequently, 11.7 parts of 1,3-propane sultone was charged into the above vessel, and the reaction was continued at 80 ° C. for 6 hours, and the reaction was terminated when the amine value of non-volatile components disappeared. After cooling to room temperature, approximately 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and isopropyl alcohol is added to the resin solution synthesized above so that the non-volatile content is 30%. Then, 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 a side chain was obtained in the same manner as the polymer (J-1) except that the raw materials described in Table 1 were changed.

The abbreviations in Table 1 are shown below.
DMAEMA: 2- (dimethylamino) ethyl methacrylate DEAEMA: 2- (diethylamino) ethyl methacrylate DMAPMA: 2- (dimethylamino) propyl methacrylate LA 82: 1,2,2,6,6-pentamethyl-4 methacrylate -Piperidyl MMA: methyl methacrylate t-BA: t-butyl acrylate HEMA: methacrylic acid 2-hydroxyethyl MAA: methacrylic acid OXMA: (3-ethyl oxetan-3-yl) methyl methacrylate MOI-BM: methacrylic acid 2- 2- (0- [1′-Methylpropylideneamino] carboxyamino) ethyl

<Production of polymer having only cationic group in side chain>
(Polymer JH-C)
100 parts of isopropyl alcohol is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen. Parts, 15 parts of dimethylaminoethyl methacrylate methyl 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 polymerization was carried out for 2 hours while maintaining this temperature. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of a comparative polymer (JH-1) having a weight average molecular weight of 7,000. After cooling to room temperature, approximately 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and isopropyl alcohol is added to the resin solution synthesized above so that the non-volatile content is 30%. Then, a polymer (JH-C) solution having only a cationic group in a side chain was prepared.

<Production of Polymer Having Only Anionic Group in Side Chain>
(Preparation of Polymer JH-A)
100 parts of isopropyl alcohol is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen. Parts, 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 2,2'-azobisisobutyro nitrile 6 .0 part of the mixed solution was added dropwise over 2 hours, and polymerization was carried out for 2 hours while maintaining this temperature. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of a 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 is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and propyl acetate is added to the resin solution synthesized previously so that the non-volatile content is 30%. Then, a comparative polymer (JH-A) solution having only an anionic group in the side chain was prepared.

The abbreviations in Table 2 are shown below.
DMCMA: dimethylaminoethyl methacrylate methyl chloride salt ATBS: acrylamido t-butyl sulfonic acid MMA: methyl methacrylate t-BA: t-butyl acrylate HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid

<Production 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 a side chain, bis (trifluoromethanesulfonyl) imide lithium: 2.79 parts (anion conversion, represented by the above-mentioned formula (2c-1) The solution was added, 117.0 parts of methanol was added, and the mixture was stirred at room temperature to dissolve it. Here, 780.0 parts of water was added dropwise over 60 minutes while stirring at room temperature, and after completion of dropping, the mixture was further stirred for 60 minutes at room temperature. Then C.I. I. 4.24 parts of basic violet 10 (cation converted, structure represented by the following formula (B-1)) is dissolved in 222.0 parts of water, and this is added dropwise over 60 minutes to the above reaction solution while stirring at room temperature The mixture was further stirred at room temperature for 60 minutes after the addition was completed. The reaction solution was dropped onto a filter paper, and it was judged that the costructured salt compound was obtained with an end point where bleeding did not occur. Thereafter, suction filtration is performed, and after washing with water, the co-structured salt compound remaining on the filter paper is dried with a dryer to remove water and dried, and a polymer (J-1) having a betaine structure in the side chain, bis ( The dye containing the polymer (A-1) which is a co-structured salt compound with trifluoromethane sulfonyl) imide lithium and Basic Violet 10 was obtained.

(Dye containing polymer (A-2) to (A-58))
Hereinafter, in the same manner as A-1 except that the polymer (J) having a betaine structure in the side chain, the cationic dye (B), and the anionic compound (Z) are changed to those shown in Table 3, Polymer (A-2) to polymer (A-58) which are costructured salt compounds of a polymer (J) having a betaine structure in a chain, a cationic dye (B) and an anionic compound (Z) The contained dye was manufactured.

Formula (SQ-1K)

Formula B-6

Formula B-9

<Production of Salt-Forming Compound of Cationic Polymer and Anionic Compound (Z)>
(Salt-forming compound (AHC-1))
To 46 parts of the polymer (JH-C) solution was added 920 parts of water, and stirring was carried out for 60 minutes at room temperature. Then, bis (trifluoromethanesulfonyl) imide lithium: 2.80 parts (anion conversion, structure represented by the formula (2c-1)) is dissolved in 140 parts of water, and this is stirred for 60 minutes in the above reaction solution at room temperature The mixture was added dropwise, and after completion of the addition, the mixture was further stirred at room temperature for 60 minutes. The reaction solution was dropped onto filter paper, and it was judged that a salt forming compound was obtained with an end point where bleeding did not occur. Thereafter, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried with a dryer to remove water and dried, and a single salt-form of polymer JH-C and trifluoromethanesulfonyl) imide lithium AHC-1 was obtained.

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

<Production of Salt-Forming Compound of Anionic Polymer and Cationic Dye (B)>
(Salt-forming compound (AHA-1))
To 46 parts of the polymer (JH-A) solution was added 920 parts of water, and stirring was carried out for 60 minutes at room temperature. Then C.I. I. Basic Violet 10: 4.44 parts (cation conversion, structure represented by the formula (B-1)) is dissolved in 222 parts of water and added dropwise to the above reaction solution over 60 minutes while stirring at room temperature After completion, the mixture was further stirred at room temperature for 60 minutes. The reaction solution was dropped onto filter paper, and it was judged that a salt forming compound was obtained with an end point where bleeding did not occur. Thereafter, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by using a dryer to remove water, and the polymer JH-A, C.I. I. An isolated salt AHA-1 with Basic Violet 10 was obtained.

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

<Production of Colored Composition for Color Filter>
Example 1
(Coloring composition CP-1)
After stirring and mixing the following mixture uniformly, after dispersing for 5 hours with an Eiger mill ("Mini model M-250MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, 5.0 μm The mixture was filtered through a filter to prepare a coloring composition (CP-1).
Dye containing polymer (A-1): 4.0 parts finely divided 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 to 82]
(Coloring composition CP-2 to 82, 101, 102)
Colored composition (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 Table 6-1 and Table 6-2. CP-2 to CP-82) were produced.

Comparative Example 1
(Coloring composition CPH-1)
After stirring and mixing the following mixture uniformly, after dispersing for 5 hours with an Eiger mill ("Mini model M-250MKII" manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, 5.0 μm The mixture was filtered through a filter to prepare a colored composition (CPH-1).
Salt-forming compound (AHC-1): 2.0 parts Salt-forming compound (AHA-1): 2.0 parts Refined 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 composition CPH-2 to CPH-10)
A coloring composition in the same manner as Comparative Example 1 except that the salt-forming compound (AHC), the salt-forming compound (AHA), the finely divided 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 produced.

<Evaluation of color composition for color filter>
About the obtained coloring composition, coating film heat resistance and storage stability (foreign material evaluation) were performed as follows. The results are shown in Tables 6-1, 6-2, and 7.

(Evaluation of heat resistance of coating film)
The resulting colored composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 20 minutes, allowed to cool By doing this, a coated substrate was produced. After the heat treatment at 230 ° C., the coated substrate was prepared, and the coating rotation number of the spin coater was adjusted so that the film thickness became 2.0 μm. The chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the obtained coating film at the C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). It measured using. Furthermore, it heats at 230 ° C. for 1 hour as a heat resistance test, and measures the chromaticity ([L ^* (2), a ^* (2), b ^* (2)]) at the C light source, according to the following formula The color difference ΔEab ^* was determined. If ΔEab ^* is less than 3.0, there is no problem in practical use. That is, evaluation 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, less than 2.0 4: 4: ΔEab ^* is 2.0 or more, less than 3.0 3: ΔEab ^* is 3.0 or more, 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 substance evaluation))
The coloring composition stored for half a year under cold storage conditions at 10 ° C. is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then 220 ° C. The coated substrate was prepared by heating and cooling for 30 minutes, and the coated substrate was observed with an optical microscope at a magnification of 500 and evaluated visually. Evaluation 3 or less which requires a treatment process is a level which is not suitable for practical use.
6: Generation of foreign matter is not observed at all 5: Generation of foreign matter is very slight 4: Generation of foreign matter is slightly recognized (level causing no problem in use)
3: Generation of foreign matter is recognized (level that can be completely removed by filtration etc. but is not suitable for practical use)
2: Occurrence of foreign matter is remarkably recognized (complete removal by filtration etc. is difficult and the level is not practical)
1: Occurrence of foreign matter is extremely high (practical level not practical)

<Production of Photosensitive Colored Composition for Color Filter>
[Embodiment 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 (manufactured by Toagosei Co., Ltd. "ALONIX M402"")
Photopolymerizable monomer 2: 1.0 part trimethylolpropane PO modified triacrylate ("Alonix M310" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator 1: 0.6 parts of ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
("IRGACURE OXE 02" manufactured by BASF Japan Ltd.)
Photopolymerization initiator 2: 0.6 parts 1- (N-4-benzoylphenyl-carbazol-3-yl) -butane-1,2-dione-2-oxime-O-acetate cyclohexanone: 5.2 parts PGMAc : 18.0 copies

[Examples 84 to 164, Comparative Examples 11 to 20]
(Photosensitive coloring composition (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 filter>
About the obtained photosensitive coloring composition, coating-film heat resistance, storage stability, developability, and glass adhesiveness evaluation were performed as follows. The results are shown in Tables 8 and 9.

(Evaluation of heat resistance of coating film)
The resulting colored composition is coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 20 minutes, allowed to cool By doing this, a coated substrate was produced. After the heat treatment at 230 ° C., the coated substrate was prepared, and the coating rotation number of the spin coater was adjusted so that the film thickness became 2.0 μm. The chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the obtained coating film at the C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). It measured using. Furthermore, it heats at 230 ° C. for 1 hour as a heat resistance test, and measures the chromaticity ([L ^* (2), a ^* (2), b ^* (2)]) at the C light source, according to the following formula The color difference ΔEab ^* was determined. If ΔEab ^* is less than 3.0, there is no problem in practical use. That is, evaluation 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, less than 2.0 4: 4: ΔEab ^* is 2.0 or more, less than 3.0 3: ΔEab ^* is 3.0 or more, 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 at 25 ° C. of the obtained photosensitive coloring composition was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Subsequently, after storing for 2 weeks in a constant temperature machine at 40 ° C. to accelerate the aging, the viscosity after aging is measured by the same method as the viscosity measurement, and the change rate of viscosity before and after storage for 2 weeks at 40 ° C. And the evaluation was made according to the following criteria. Evaluation 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% ± 5% or less 4: Viscosity change rate is more than ± 5% ± 10% or less 3: Viscosity change rate is ± 10% Exceeding ± 20% or less 2: Viscosity change rate exceeds ± 20% ± 30% or less 1: Viscosity change rate exceeds ± 30%

(Developability evaluation)
The photosensitive coloring composition was coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater and heated in a clean oven at 70 ° C. for 15 minutes to remove the solvent and obtain a coated film. . Subsequently, ultraviolet light exposure was performed with an integrated light quantity of 200 mJ / cm ² using an extra-high pressure mercury lamp, 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 formation was possible without the development remaining was taken as the development dissolution time, and the evaluation was made based on the following criteria. Evaluation 3 or less is a level unsuitable for practical use.
6: development dissolution time less than 25 s 5: development dissolution time 25 s to less than 30 s 4: development dissolution time 30 s to less than 40 s 3: development dissolution time 40 s to less than 60 s 2: development dissolution time 60 s to less than 80 s 1: When the pattern does not remain peeled even if the development dissolution time is 80s or more or less than 80s

(Glass adhesion evaluation)
The substrate coated with the photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotational speed of 2 μm after drying is dried at 70 ° C. for 20 minutes An ultraviolet light of 150 mJ / cm ² was irradiated using a super high pressure mercury lamp through a photomask having 100 openings of 10 μm × 10 μm. Next, after spray development was performed using an alkaline developer consisting of a 0.2% aqueous solution of sodium carbonate to remove an unexposed portion, the resultant was washed with ion exchanged water. At this time, the adhesion was evaluated based on how many 10 μm × 10 μm patterns remain. Further, the evaluation of developability was judged according to the following criteria. Evaluation 3 or less is a level unsuitable for practical use.
6: 95 or more patterns remaining 5: 90 to 95 patterns remaining 4: 80 to 89 patterns remaining 3: 70 to 79 patterns remaining 2: 50 ~ 69 patterns left 1: 50 patterns or less

<Preparation of color filter>
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (CR-29) was coated on the substrate to a thickness of x = 0.640 by a spin coater to form a colored film. The film was irradiated with ultraviolet light of 300 mJ / cm ² through a photomask using an extra-high pressure mercury lamp. Next, after spray development with an alkaline developer consisting of a 0.2% aqueous solution of sodium carbonate to remove an unexposed area, the substrate is washed with ion exchanged water and heated at 230 ° C. for 20 minutes to form a red filter segment. It formed. Next, a green photosensitive segment is formed to a thickness such that y = 0.600 using a green photosensitive colored composition (CR-32) by the same method, and a blue photosensitive colored composition is further produced by the same method. A blue filter segment was formed to a film thickness such that y = 0.060, and the product (CR-27) was coated to obtain a color filter.

By using the coloring composition of the present invention, the heat resistance of the color filter was improved, and the developability and the adhesion to glass were good, and the other physical properties could be suitably used without any problem.

Claims (8)

A coloring composition for a color filter comprising a coloring agent, a binder resin and an organic solvent, wherein the coloring agent contains a polymer (A) containing at least a repeating unit represented by the following general formula (1) There are coloring compositions for color filters.
General formula (1)

[In the 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 ^- is a monovalent anionic group.
B ⁺ is a cation derived from a cationic dye,
Z ⁻ is derived from an anionic compound,
An anion represented by the following general formula (2a),
An 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, Hal represents a halo group, and when a plurality of R ¹ and Hal are present, they may be the same or different. It is also good. c shows the integer of 0-6. ]

[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 And R ² and Hal may be the same or different when there are a plurality of groups. d shows the integer of 0-4. ]

[In general formula (2c), R ³ and R ⁴ each independently represent a halogenated hydrocarbon group which may be linked by a sulfonyl group, a cyano group or a FSO ₂ group, and R ³ and R ⁴ are both sulfonyl When it is a halogenated hydrocarbon group which may be linked by a group, it may combine with 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 which may be linked by a linking group having a nitrogen atom or an oxygen atom. ]
The coloring composition for color filters 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 to R ¹² and * ² represents a bond to 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 to R ¹² and * ² represents a bond to R ¹³ . ] The coloring composition for color filters according to claim 2, wherein X ⁺ in the general formula (1) is a divalent linking group represented by the general formula (2). Formula in (1) Y ^- is, -CO ₂ ^- or SO ₃ ^- for a color filter coloring composition according to any one of claims 1 to 3, a.   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 color filters according to any one of claims 1 to 5, wherein the coloring agent further comprises a pigment.   The coloring composition for color filters 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 of the coloring composition for color filter according to any one of claims 1 to 7.