JP2021081574A - Color filter coloring composition and color filters - Google Patents

Abstract

To provide a color filter coloring composition which enables expression of a high transmittance spectrum inherent to a dye in a color filter coating film and offers superior filterability required in a color filter manufacturing process, and to provide a color filter using the same.SOLUTION: The above mentioned problem is solved by a color filter coloring composition containing a colorant, binder resin and organic solvent, where the colorant comprises a dye containing a polymer (A) having at least a specific repeating unit.SELECTED DRAWING: None

Description

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

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

As a method for producing a color filter, a dyeing method for dyeing a pattern after forming a pattern with a photoresist, or a pigment-containing resin in which a transparent electrode having a predetermined pattern is formed in advance and dissolved and dispersed in a solvent by applying a voltage is used. Electrodeposition method for ionizing and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material The method is known, and recently, the pigment dispersion method has become the mainstream. However, a color filter using a pigment as a colorant disturbs the degree of polarization controlled by the liquid crystal due to scattering of light by the pigment particles and the like, and as a result, the contrast of the color liquid crystal display device is likely to be lowered. There's a problem. Furthermore, since the pigment exists in a particle state, there is a limit to the sharpening of the spectral shape, and it is difficult to increase the brightness from the current state. Therefore, in recent years, attention has been focused on dye-based colorants in order to achieve high brightness and high contrast ratio that cannot be achieved with pigments.

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

Therefore, in order to improve the solubility in an organic solvent, a color filter using a salt-forming compound of a cationic dye and an anionic compound which is a strong acid as a colorant has been proposed (Patent Documents 1 to 4). ). In general, it is known that the solubility of a cationic dye in an organic solvent is improved by replacing the counter anion (Cl ^{− or the like) of the cationic dye with an anion derived from an anionic compound.} This makes it possible to improve the brightness as compared with the pigment type. However, in the above method, the compatibility with the main resin used when producing the color filter is also poor, and a part of the dye is in an aggregated state in the coating film of the color filter, which is expressed when the dye is in a state close to a monomolecular state. It was not possible to obtain a steep and highly transmissive spectrum, and it was not possible to sufficiently draw out the lightness potential of the dye when the color filter was formed.

Meanwhile, in order to improve the heat and light resistance, coloring composition is chemically bonded dye to the polymer (see Patent Document 5-6) and an anionic substituent cationic dye in the side chain (-SO 3 _H and the like A colored composition obtained by salt formation with a polymer having (Patent Document 7) has been proposed. However, the coloring composition also has poor compatibility with the main resin used when producing the color filter, and a part of the dye is aggregated in the coating film of the color filter, so that the dye is close to a monomolecular state. It was not possible to obtain the steep, high-transmittance spectroscopy that appears in the situation, and it was not possible to draw out the lightness potential of the dye when the color filter was formed.

Further, the coloring composition for a color filter and the photosensitive coloring composition for a color filter in which a dye and a pigment are used in combination are filtered to remove foreign substances when the dye is dissolved in a solvent to prepare a dye solution. At present, since dissolution at a high concentration is required, it is known that the dye does not dissolve sufficiently and becomes aggregated and clogs the filter, so that the filterability becomes an issue. For example, there is a technique for improving the filterability by a method for producing a dye dispersion (Patent Document 8). However, although this document describes the increase in brightness from pigments, it does not mention the technique for drawing out the original brightness potential of dyes.
Since this technique uses a tertiary amine, the acid-base interaction with the acid dye is relatively weak, and the stability over time tends to be relatively poor.

As described above, it has been difficult with known techniques to maximize the lightness potential of the dye in the color filter coating film and to achieve both the filterability of removing foreign substances in the manufacturing process of the color filter.

Japanese Unexamined Patent Publication No. 2013-067776 Japanese Unexamined Patent Publication No. 2012-107192 Japanese Unexamined Patent Publication No. 2012-173399 Japanese Unexamined Patent Publication No. 2013-163804 Japanese Unexamined Patent Publication No. 2000-162429 Japanese Unexamined Patent Publication No. 2012-032754 Japanese Unexamined Patent Publication No. 2013-137502 Japanese Unexamined Patent Publication No. 2013-213161

The present invention is a coloring composition for a color filter that expresses the high transmittance spectrum inherent in a dye in a color filter coating film and has excellent filterability required in the manufacturing process of a color filter, and a color filter using the same. The purpose is to provide.

As a result of diligent research to solve the above problems, the present inventors have obtained a coloring composition for a color filter containing a coloring agent, a binder resin and an organic solvent, and the coloring agent has at least the following general formula ( A coloring composition for a color filter containing a dye containing a repeating unit represented by 1) and a polymer (A) containing a repeating unit represented by the following general formula (2) is highly transmissive. The present invention has been made based on this finding, which has been found to exhibit rational spectroscopy in a color filter coating film and to exhibit excellent filterability.

That is, the present invention is a coloring composition for a color filter containing a colorant, a binder resin and an organic solvent, wherein the colorant is at least a repeating unit represented by the following general formula (1), and the following general formula (2). The present invention relates to a coloring composition for a color filter, which comprises a dye containing a polymer (A) containing a repeating unit represented by).

［一般式（１）において、Ｒ^１１は水素原子またはメチル基を表し、Ｒ^１２およびＲ^１３はそれぞれ独立に、２価の連結基を表し、Ｘ^＋は２価のカチオン性連結基を表し、Ｙ⁻は１価のアニオン性基を表す。Ｂ⁺は、カチオン性染料由来のカチオンであり、Ｚ⁻はアニオン性化合物由来のアニオンを表す。ただし、前記カチオン性染料は、キサンテン系染料、トリフェニルメタン系染料、およびシアニン系染料からなる群から選ばれる少なくとも１種である。］

一般式（２）

［一般式（２）において、Ｒ^２１は水素原子またはメチル基を表し、Ｒ^２２は炭素数６以上の直鎖状、分岐状、又は環状の炭化水素基を表す。］
General formula (1)

[In general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. Y ⁻ represents a monovalent anionic group. B ⁺ is a cation derived from a cationic dye, and Z ⁻ represents an anion derived from an anionic compound. However, the cationic dye is at least one selected from the group consisting of xanthene dyes, triphenylmethane dyes, and cyanine dyes. ]

General formula (2)

[In the general formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a linear, branched, or cyclic hydrocarbon group having 6 or more carbon atoms. ]

The present invention also relates to the above-mentioned coloring composition for a color filter having a hydrocarbon group having 10 or more carbon atoms in the general formula (2).

Further, in the present invention, in the polymer (A), the weight of the portion of the polymer (A) excluding the cation represented by ^{B + and the anion represented by Z − in the general formula (1) is determined.} The present invention relates to the above-mentioned coloring composition for a color filter, wherein the content of the repeating unit represented by the general formula (2) is 10 to 50% by weight when the content is 100% by weight.

The present invention also relates to the above-mentioned coloring composition for a color filter, wherein the binder resin contains a repeating unit represented by the general formula (2).

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

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

INDUSTRIAL APPLICABILITY According to the present invention, a coloring composition for a color filter, which expresses the high transmittance spectrum inherent in a dye in a color filter coating film and has excellent filterability required in a color filter manufacturing process, and a color filter using the same. Can be provided.

Hereinafter, the constituent requirements of the present invention will be described in detail.
In the present application, when "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", or "(meth) acrylate" is described, unless otherwise specified, "(meth) acrylate" is used. It shall represent "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", or "acrylate and / or methacrylate". Further, "CI" mentioned in the present specification means a color index (CI).

The coloring composition for a color filter of the present invention contains a colorant, a binder resin and an organic solvent, and the colorant is represented by at least a repeating unit represented by the following general formula (1) and the following general formula (2). It contains a dye containing a polymer (A) containing a repeating unit, and the dye contains at least one selected from the group consisting of xanthene dyes, triphenylmethane dyes, and cyanine dyes. It is a feature.

<Coloring composition for color filters>
<Colorant>
The colorant in the present invention contains a dye containing a polymer (A) containing at least a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). The dye containing the polymer (A) is a cation of a resin having an amphoteric ionic structure (betaine structure) having a cationic moiety and an anionic moiety in the same molecule in the repeating unit represented by the general formula (1). It has a salt-forming structure in which an ^{anion Z −} derived from an anionic compound ^{is selectively co-salted with a cation B +} derived from a cationic dye at the anionic site. As a result, it has high storage stability and heat resistance, and also has excellent alkali solubility (developability) and glass adhesion. Further, the colorant may contain other colorants such as organic pigments and dyes.

[Polymer (A) containing repeating units represented by the general formula (1) and the general formula (2)]
(General formula (1))
The general formula (1) will be described in detail.

［一般式（１）において、Ｒ^１１は水素原子またはメチル基を表し、Ｒ^１２およびＲ^１３はそれぞれ独立に、２価の連結基を表し、Ｘ^＋は２価のカチオン性連結基を表し、Ｙ⁻は１価のアニオン性基を表す。Ｂ⁺は、カチオン性染料由来のカチオンであり、Ｚ⁻はアニオン性化合物由来を表す。ただし、前記カチオン性染料は、キサンテン系染料、トリフェニルメタン系染料、およびシアニン系染料からなる群から選ばれる少なくとも１種である。］ General formula (1)

[In general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. Y ⁻ represents a monovalent anionic group. B ⁺ is a cation derived from a cationic dye, and Z ⁻ represents an anionic compound. However, the cationic dye is at least one selected from the group consisting of xanthene dyes, triphenylmethane dyes, and cyanine dyes. ]

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

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

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

The arylene alkandyl group is a divalent group formed by combining an arylene group and an alkandyl group. For example, a phenylene methylene group, a phenylenedi methylene group, a phenylene trimethylene group, a phenylene tetramethylene group and a phenylene pentamethylene group. _{, Phenylene C 1-6} alcandiyl group such as phenylene hexamethylene group can be mentioned.

Further, at least one selected from an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms, and -O-, -S-, -COO-, and -CONRb- (Rb is a hydrogen atom or carbon). (Indicating an alkyl group having a number of 1 to 8) and ^{at least one selected from SO 2-} ), the group composed of a combination thereof includes an alkanediyl group having 1 to 10 carbon atoms and an arylene group having 6 to 20 carbon atoms. A group consisting of a combination of at least one selected and at least one selected from -O-, -COO- and SO ^2- is preferable, and an alkanediyl group having 1 to 10 carbon atoms and an arylene having 6 to 20 carbon atoms are preferable. More preferably, a group consisting of a combination of at least one selected from the groups and at least one selected from -O- and SO ^2-. Specific examples of the alkyl group having 1 to 8 carbon atoms according to Rb include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a hexyl group. , Heptyl group, octyl group and the like.

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

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

Further, ^{as the divalent linking group in R 13,} an alkanediyl group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an arylene alkanediyl group having 7 to 20 carbon atoms is preferable, and the arylene alkanediyl group having 7 to 20 carbon atoms is preferable. The alkanediyl group of ~ 5 is more preferable, and a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group and a pentane-1,5-diyl group are further preferable.

(X ⁺ : cationic divalent linking group)
^{The cationic divalent linking group in X +} of the general formula (1) is represented by the following general formula (3), the following general formula (4) or P ⁺ (R ²⁰¹ ) (R ²⁰² ) −, and the like. Group is mentioned. R ²⁰¹ and R ²⁰² each independently represent a monovalent organic group.

General formula (3)

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

General formula (4)

[In the general formula (4), R ¹⁶ and R ¹⁷ each independently represent a monovalent organic group.
* ¹ represents a bond with R ^{12 and * 2} represents a bond with R ¹³ . ]

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

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

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

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

The cationic divalent linking group in X ⁺ is preferably a group represented by the general formula (3) or the general formula (4), and more preferably a group represented by the general formula (3). is there. Further, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are preferably monovalent aliphatic hydrocarbon groups, more preferably monovalent aliphatic hydrocarbon groups having 1 to 5 carbon atoms, and further preferably. Is a methyl group or an ethyl group, particularly preferably a methyl group.

(Y ⁻ : anionic monovalent group)
Examples of the anionic monovalent group in ^{Y −} of the general formula (1) _{include CO 2} ⁻ , SO ₃ ^−, H ₂ PO ₄ ^−, etc., but from the viewpoint of availability of raw materials and heat resistance, CO ₂ ⁻ or SO ₃ ⁻ is preferable, and SO ₃ ⁻ is particularly preferable.

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

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

The present invention is characterized in that at least one of a xanthene-based cationic dye, a triphenylmethane-based cationic dye, and a cyanine-based cationic dye is used as the structure of the cationic dye. By using the above dye, the optical characteristics required for color filter applications are improved. Among them, cyanine dyes are more preferable because they show the best optical properties.

Specific examples of cationic dyes that can be used for the synthesis of salt-forming compounds are shown below by color index numbers.

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

Examples of the xanthene-based cationic dye include C.I. I. Basic Red 1 (Rhodamine 6G, 6GCP), 3 and 8 (Rhodamine G), and the like can be mentioned. Above all, C.I. It is preferable to use I. Basic Red 1.

Examples of the cyanine-based cationic dye include C.I. I. Basic Yellow 11, 21, 28, etc. can be mentioned.

It is also preferable to use a cyanine-based cationic dye having the following chemical formula.

As the cationic dye, in addition to the above dyes, other cationic dyes can also be used in combination. For example, anthraquinone-based cationic dyes, auramine-based cationic dyes, flavin-based cationic dyes, safranin-based cationic dyes, acrydin-based cationic dyes, oxazine-based cationic dyes, thiazine-based cationic dyes, methylene blue-based cationic dyes, Examples thereof include monoazo-based cationic dyes, disazo-based cationic dyes, oxazine-based cationic dyes, aminoketone-based cationic dyes, quinoline-based cationic dyes, and squarylium-based cationic dyes.

Specific examples of dyes that can be used together are given below. Examples of the anthraquinone-based cationic dye include C.I. I. Basic Blue 72, as a flavin-based cationic dye, C.I. I. Basic Yellow 1, as an auramine-based cationic dye, C.I. I. Basic Yellow 2, 3, Safranin-based cationic dyes include C.I. I. Basic Red 2, as an acridine-based cationic dye, C.I. I. Basic Yellow 5, as an oxazine-based cationic dye, C.I. I. Basic Blue 3, thiazine-based cationic dyes include C.I. I. Basic Blue 24, as a methylene blue-based cationic dye, C.I. I. Basic blue 9 (methylene blue FZ, methylene blue B), 25 (basic blue GO), 24 (new methylene blue NX) and the like can be mentioned. Above all, C.I. I. It is preferable to use Basic Yellow 1, Blue 9, 24, and 25.

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

(Anion derived from the anionic compound ^(Z -))
^{The anionic compound in Z −} of the general formula (1) is not particularly limited as long as it is an anionic compound ionically bonded to the precursor zwitterionic resin, and is suitable for the production process of the salt-forming compound, an organic solvent and development. It can be appropriately selected in consideration of all required performances such as solubility in a liquid, salt forming property, absorbance, interaction with other components in the present composition, light resistance, and heat resistance. Among them, from the viewpoint of solubility in an organic solvent, light resistance and heat resistance, anions represented by the following general formulas (5a) to (5d) are preferable.

(Anion represented by the general formula (5a))

General formula (5a)
[(R ¹ ) _c P Hal _6-c ] ^-

[In the general formula (5a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, H represents a halo group, and ^{when a plurality of R 1} and H are present, they are the same but different. May be good. c represents an integer from 0 to 6. ]

Examples of the Hall of the general formula (5a) include a fluoro group, a chloro group, a bromo group, and an iodine group, and a fluoro group is preferable.

^{The halogenated hydrocarbon group in R 1} of the general formula (5a) is preferably an alkyl group substituted with a halogen atom or an aryl group substituted with a halogen atom, and more preferably an alkyl fluoride group or an aryl fluoride. It is a group. A aryl fluoride group is more preferable, and a pentafluorophenyl group is particularly preferable.

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

(Anion represented by the general formula (5b))

General formula (5b)
^{_{[(R 2) d B Hal}} 4-d] -

[In the general formula (5b), 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. It represents a group, if R ^2, Hal there are a plurality each of which may be the same or different. d represents an integer from 0 to 4. ]

Hal of the general formula (5b) is synonymous with Hal of the above-mentioned general formula (5a).

R ² represents a halogenated hydrocarbon group, a cyano group or a nitro group or a phenyl group substituted with a nitro group, and the halogenated hydrocarbon group is a halogenated hydrocarbon as ^{Z − in the above general formula (5a).} The halogenated hydrocarbon group mentioned in the description of the anion having a hydrogen group can be mentioned. In the present invention, R ² is preferably a halogenated hydrocarbon group, preferably an alkyl fluoride group, or preferably an aryl fluoride group.

^{The halogenated hydrocarbon group in R 2} of the general formula (5b) is synonymous with the halogenated hydrocarbon group in ^{R 1} of the general formula (5a) described above. R ² is preferably a halogenated hydrocarbon group, preferably an alkyl fluoride group or an aryl fluoride group.

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

(Anion represented by the general formula (5c))

General formula (5c)
R ³ −N ⁻ −R ⁴

[In general formula (5c), R ³ and R ⁴ each independently represent a halogenated hydrocarbon group, a cyano group or _two ^{FSO groups which may be linked by a sulfonyl group, and both R 3} and R ⁴ are sulfonyl groups. In the case of halogenated hydrocarbon groups which may be linked by a group, they may be bonded to each other to form a ring. However, ^{at least one of R 3} and R ⁴ is a halogenated hydrocarbon group or a cyano group. ]

^{The halogenated hydrocarbon group in R 3} and R ⁴ of the general formula (5c) is synonymous with the halogenated hydrocarbon group in ^{R 1} of the general formula (5a) described above. Further, R ³ and R ⁴ may form a cyclic structure of an aliphatic saturated hydrocarbon system. The sulfonyl group in the halogenated hydrocarbon group which may be linked with a sulfonyl group is a linking group of N ⁻ and R ³ or N ⁻ and R ⁴ . R ³ and R ⁴ are preferably halogenated hydrocarbon groups that are independently linked by a sulfonyl group, more preferably a fluorinated alkylsulfonyl group or a fluorinated arylsulfonyl group, and are particularly excellent in heat resistance. Become.

Typical examples of the anion represented by the general formula (5c) are [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , [(FSO ₂ ) N (CF). ₃ CF ₂ SO ₂ )] ^- , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ^- , [(FSO ₂ ) N (CF ₃ CF ₂ CF ₂ SO ₂ )] ^- , [(FSO ₂₎ ) N (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFCF ₂ SO ₂ }] ⁻ , [(FSO ₂ ) N {CF ₃ CF ₂ (CF) ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ⁻ , [(CF ₃ SO ₂ ) ₂ N] ⁻ , [(CF ₃ CF ₂ SO ₂ ) ₂ N] ^- , [(CF ₃ CF ₂ CF ₂ SO ₂ ) ₂ N] ^- , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₂ N] ^- , [{(CF ₃ ) ₂ CFCF ₂ SO ₂ } ₂ N] ⁻ , [{CF ₃ CF ₂ (CF ₃ ) CFSO ₂ } ₂ N] ⁻ , [{(CF ₃ ) ₃ CSO ₂ } ₂ N] ⁻ , or the following compounds can be mentioned.

(Anion represented by the general formula (5d))

General formula (5d)
R ⁵ -SO ₃ ^-

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

^{The halogenated hydrocarbon group in R 5} of the general formula (5d) is synonymous with the halogenated hydrocarbon group in ^{R 1} of the general formula (5a) described above. Halogenated hydrocarbon groups may be linked by -O-, -CO-, -COO-, -CO-NH- or the like.
R ⁵ is preferably a halogenated hydrocarbon group, more preferably a fluorinated alkylsulfonyl group or a fluorinated arylsulfonyl group, and is particularly excellent in heat resistance.

As a typical example of the anion represented by the general formula (5d), for example, the anion represented by the following can be mentioned.

^{The Z −} of the general formula (1) is preferably an anion represented by the general formula (5b) or (5c). In addition, specific examples of anions that can be preferably used are shown below.

式（５ｂ−１）：（一般式（５ｂ）で表されるアニオンに該当）

式（５ｂ−２）：（一般式（５ｂ）で表されるアニオンに該当）

Formula (5a-1): (corresponds to the anion represented by the general formula (5a))

Formula (5b-1): (corresponds to the anion represented by the general formula (5b))

Formula (5b-2): (corresponds to the anion represented by the general formula (5b))

式（５ｃ−２）：（一般式（５ｃ）で表されるアニオンに該当）

式（５ｃ−３）：（一般式（５ｃ）で表されるアニオンに該当）

式（５ｄ−１）：（一般式（５ｄ）で表されるアニオンに該当）

Formula (5c-1): (corresponds to the anion represented by the general formula (5c))

Formula (5c-2): (corresponds to the anion represented by the general formula (5c))

Formula (5c-3): (corresponds to the anion represented by the general formula (5c))

Formula (5d-1): (corresponds to the anion represented by the general formula (5d))

［一般式（２）において、Ｒ^２１は水素原子またはメチル基を表し、Ｒ^２２は炭素数６以上の直鎖、分岐状、又は環状の炭化水素基を表す。］ (General formula (2))
The general formula (2) will be described in detail.
General formula (2)

[In the general formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a linear, branched or cyclic hydrocarbon group having 6 or more carbon atoms. ]

The hydrocarbon group having a linear structure and a branched structure having 6 or more carbon chains includes, for example, a hexyl group, a heptyl group, an octyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group and a hexadecyl group. , Heptadecyl group, octadecyl group, nonadecil group, icosyl group, henicosyl group, docosyl group, tricosyl group, alkyl group of tetracosyl group and the like. As the hydrocarbon group having a linear structure and a branched structure, a branched structure is preferable, and an isostearyl group is more preferable. When the number of carbon atoms of the hydrocarbon groups in the linear structure and the branched structure is 6 or more, the effect of the present invention can be seen, but when it is 10 or more, the effect becomes remarkable, which is preferable. The carbon chain is preferably 30 or less.

Examples of the hydrocarbon group having a cyclic structure (also referred to as a cyclic hydrocarbon group) include an alicyclic hydrocarbon group and a polycyclic hydrocarbon group.
Examples of the alicyclic hydrocarbon group include a cyclododecyl group and the like.
Examples of the polycyclic hydrocarbon group include an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group and the like. As these alicyclic hydrocarbon group and polycyclic hydrocarbon group, a polycyclic hydrocarbon group is preferable, and a dicyclopentanyl group is more preferable.

[Method for producing polymer (A) containing repeating units represented by general formulas (1) and (2)]

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

The repetition represented by the general formula (2) is carried out in the polymer (A) excluding the cationic dye represented by ^{B + and the anionic compound represented by Z − in the general formula (1).} , 5 to 70% by weight, the effect of the present invention can be sufficiently exhibited. Further, when it is contained in an amount of 10 to 50% by weight, the effect becomes remarkable, which is preferable.

The polymer (A) containing the repeating unit represented by the general formula (1) and the general formula (2) can be synthesized by using a known synthesis method. An example of the synthesis method will be described below.

(Method for producing an amphoteric ion resin which is a precursor of the polymer (A))
The zwitterionic resin, which is a precursor of the polymer (A), can be synthesized by using a known synthetic method. Preferred production methods include the following methods (i) and (ii).

≪Manufacturing method (i) ≫
An ethylenically unsaturated monomer (b1) which is a precursor of a repeating unit represented by the general formula (1) and an ethylenically unsaturated monomer which is a precursor of a repeating unit represented by the general formula (2). A method of polymerizing a body (b5) and another ethylenically unsaturated monomer (b3) by a known polymerization reaction.

≪Manufacturing method (ii) ≫
An ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4), an ethylenically unsaturated monomer (b5) which is a precursor of a repeating unit represented by the general formula (2), and others. A method of reacting a modified species (b4) with an intermediate polymer (a) obtained by a known polymerization reaction with an ethylenically unsaturated monomer (b3).
Each manufacturing method will be described below.

≪Manufacturing method (i) ≫
Examples of the ethylenically unsaturated monomer (b1) which is a precursor of the repeating unit represented by the general formula (1) include a monomer represented by the following general formula (6).

(Ethylene unsaturated monomer (b1))
General formula (6)

[In the general formula (6), 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 (7) or It represents a group represented by the general formula (8), and Y ⁻ represents CO ₂ ⁻ or SO ₃ ⁻ . ]

General formula (7)

[In the general formula (7), 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 (8)

[In the general formula (8), R ⁶¹ and R ⁶² each independently represent a monovalent organic group.
* ¹ represents a bond with R ^{42, and * 2} represents a bond with R ⁴³ . ]

^{The divalent linking group in R 42} and R ⁴³ of the general formula (6) is synonymous with the divalent linking group in ^{R 12} and R ¹³ of the general formula (1).

^{The monovalent organic group in R 51} and R ⁵² of the general formula (7) is synonymous with the monovalent organic group in ^{R 14} and R ¹⁵ of the general formula (3).

^{The monovalent organic group in R 61} and R ⁶² of the general formula (8) is synonymous with the monovalent organic group in ^{R 16} and R ¹⁷ of the general formula (4).

Examples of the compound represented by the general formula (6) include compounds represented by the following (6-1 to 6-24).

Among them, compounds (6-1), (6-2), (6-9), (6-10), (6-11), (6-12), (6-17), (6-18), (6-21), (6-22), (6-23) are preferable, and (6-1), (6-2), (6-9), (6-10), (6-) are more preferable. 11), (6-12), (6-23), more preferably (6-9), (6-10), (6-11), (6-12), (6-23). Yes, most preferably (6-9), (6-10).

Examples of the ethylenically unsaturated monomer (b5) which is a precursor of the repeating unit represented by the general formula (2) include a monomer represented by the following general formula (9).

［一般式（９）において、Ｒ^９１は水素原子またはメチル基を表し、Ｒ^９２は炭素数６以上の直鎖、分岐状、又は環状の炭化水素基を表す。］ (Ethylene unsaturated monomer (b5))
General formula (9)

[In the general formula (9), R ⁹¹ represents a hydrogen atom or a methyl group, and R ⁹² represents a linear, branched or cyclic hydrocarbon group having 6 or more carbon atoms. ]

^{R 91} and R ⁹¹ of the general formula (9) are synonymous with ^{R 21} and R ²² of the general formula (2).

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

Carboxylic acid-containing ethylenically unsaturated monomers include, for example, acrylic acid, methacrylic acid, ε-couplerolactone-added acrylic acid, ε-couplerolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples include acid.

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

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

≪Manufacturing method (ii) ≫
Examples of the ethylenically unsaturated monomer (b2) capable of reacting with the modified species (b4) include a monomer represented by the following general formula (10).

(Ethylene unsaturated monomer (b2))
General formula (10)

[In the general formula (10), R ⁷¹ represents a hydrogen atom or a methyl group, and R ⁷² represents a divalent organic group. Z represents -N (R ⁷³ ) (R ⁷⁴ ), or P (R ⁷⁵ ) (R ⁷⁶ ), or a group represented by the following general formula (11), and R ^{73 to} R ⁷⁶ are independent of each other. Indicates a monovalent organic group. ]

General formula (11)

[In the general formula (11), R ⁸¹ and R ⁸² each independently represent a monovalent organic group. ]

^{The divalent organic group in R 72} of the general formula (10) is synonymous with the divalent linking group in ^{R 12} of the general formula (1).
^{The monovalent organic group in R 73 to} R ⁷⁶ of the general formula (10) is synonymous with the monovalent organic group in the general formulas (3) and (4).
^{The monovalent organic group in R 81} and R ⁸² of the general formula (11) is synonymous with the monovalent organic group in ^{R 16} and R ¹⁷ of the general formula (4).

The ethylenically unsaturated monomer (b2) represented by the general formula (10) is, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-. Secondary such as dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, 2,2,6,6-tetramethylpiperidyl methacrylate, 1,2,2,6,6-pentamethylpiperidyl methacrylate Or (meth) acrylates having a tertiary amino group;
Tertiary such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. (Meta) acrylamides having an amino group; and the like. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (methacrylate), N, N-dimethylaminopropyl (meth) acrylamide, 1,2,2,6,6-pentamethyl Piperidyl methacrylate is preferred, and 1,2,2,6,6-pentamethyl piperidyl methacrylate is more preferred.

(Ethylene unsaturated monomer (b5))
The ethylenically unsaturated monomer (b5), which is a precursor of the repeating unit represented by the general formula (2), has the same meaning as the ethylenically unsaturated monomer (b5) in the production method (i).

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

(Denatured species (b4))
As the modified species (b4), if it can react with Z in the general formula (10) which is a constituent monomer of the polymerized intermediate polymer (a) and gives the structure of the general formula (1) after the reaction. The present invention is not particularly limited, and examples thereof include a compound represented by the following general formula (12), a compound represented by the following general formula (13), and the like.

General formula (12) X- (CH ₂ ) _n- Q
[In the general formula (12), 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 (13)

[In general formula (13), 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 (12) include chloroacetic acid, fluorinated acetic acid, bromoacetic acid, iodoacetic acid, chloropropionic acid, fluorinated propionic acid, bromopropionic acid, iodopropionic acid, chlorobutanoic acid and fluoride. Butanoic acid, bromobutanoic acid, iodobutanoic acid chloromethanesulfonic acid, methylfluorosulfonic acid, bromomethanesulfonic acid, iodomethanesulfonic acid, chloropropanesulfonic acid, propanesulfonic acid fluoride, bromopropanesulfonic acid, iodopropanesulfonic acid, chloro Butane sulfonic acid, butane fluorinated acid, bromobutane sulfonic acid, iodobutane sulfonic acid chloromethanephosphonic acid, methyl fluorinated phosphonic acid, bromomethanephosphonic acid, iodomethanephosphonic acid, chloropropanephosphonic acid, chloropropanephosphonic acid, bromo Propanephosphonic acid, iodopropanephosphonic acid, chlorobutanephosphonic acid, butanefluorinated butanephosphonic acid, bromobutanephosphonic acid, iodobutanephosphonic acid and the like can be mentioned, but bromoacetic acid, chloropropionic acid and chloroacetic acid are preferable, and chloroacetic acid is particularly preferable. Is particularly preferred.

Examples of the compound represented by the general formula (13) include propane sultone, butane sultone, α-acetolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone ε-caprolactone. Of these, propane sultone and butane sultone are preferable.

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

Further, the zwitterionic resin which is a precursor of the polymer (A) suitable for the present invention preferably has a property of being dissolved in a solvent widely used in a coloring composition for a color filter. As a result, a coating film that does not generate foreign matter can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

In the zwitterionic resin which is a precursor of the polymer (A), it is represented by excluding the cationic dye represented by ^{B + and the anionic compound represented by Z − in the above general formula (1).} The total content of the structural units is not particularly limited, but when all the structural units contained in the structural units are 100% by weight, the above general is considered from the viewpoint of solvent solubility and coloring power of the salt-forming compound. The total content of the structural units represented by the formula (1) excluding the cationic dye represented by ^{B + and the anionic compound represented by Z − is preferably 5% by weight or more.} , 10 to 50% by weight, more preferably 15 to 40% by weight. When an appropriate amount is contained, the adhesion to the base material and various durability of the coating film are further improved.

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

^[- method for producing salt-forming compound consisting of polymer (A) and the dye (B) and an anionic compound (Z)]
The polymer (A) of the present invention is a solution prepared by dissolving an amphoteric ionic resin which is a precursor of the polymer (A) in water or a water-soluble solvent, and the general formulas (5a) to (5d) of the present application. An anionic compound having an anion (Z ⁻ ) represented by (Z −) and a solution dissolved in water or a water-soluble solvent are mixed and stirred, and then a cationic dye having ^{a cation (B +) of the present application is used.} It can be easily obtained by dropping a solution dissolved in dissolved water or a water-soluble solvent, mixing and stirring. In the aqueous solution, the cationic group of the amphoteric ionic resin and the specific anion (Z ⁻ ) of the anionic compound of the present application, and the anionic group of the amphoteric ionic resin and the cation of the cationic dye (B ⁺ ) are ionic bonded, respectively. As a result, it becomes water-insoluble and the salt-forming compound is precipitated. The anionic compound and the cationic dye may be used in the reverse order, and the amphoteric resin, the anionic compound, and the cationic dye to be used may be used alone or in multiple types having different structures. You may.

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

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

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

Examples of the green coloring composition for forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63 and other green pigments can be used. Further, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment and the like described in JP-A-2004-333817, Patent No. 4893859 and the like can also be used. Further, the green coloring composition includes C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or 231 can be used in combination.

The blue coloring composition for forming the blue filter segment includes, for example, C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: Blue pigments such as 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. Can be used. Further, the blue coloring composition includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and other purple pigments can be used in combination. Further, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment and the like described in JP-A-2004-333817, Patent No. 4893859 and the like can also be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

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

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

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins in which an unsaturated ethylenically double bond is introduced by the methods (a) to (c) shown below.

[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 with one or more other types of monomers can be used. , The carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added and reacted, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

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

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

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

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

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

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

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

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

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

Since the binder resin has good film forming properties and various resistances, it is preferable to use the binder resin in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight), and the colorant concentration is high and good. Since it can exhibit color characteristics, it is preferably used in an amount of 500% by weight or less.

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

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

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl-. 1,3-Propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, Isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol mono Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Propylene acetate, dibasic acid ester and the like.

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

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

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

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

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

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

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

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

Photopolymerization initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetphenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4 Benzophenone compounds such as'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6 -Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4 Triazine compounds such as -trichloromethyl- (4'-methoxystyryl) -6-triazine; 1- (N-4-benzoylphenyl-carbazole-3-yl) -butane-1 , 2-Dione-2-oxime-O-acetate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4') -Oxime ester compounds such as methoxy-naphthyl) ethylidene) hydroxylamine; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9 , 10-Fenancelenquinone, camphorquinone, ethylanthraquinone and other quinone compounds; borate compounds; carbazole compounds; imidazole compounds; or titanosen compounds are used.

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

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

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

In addition, "Handbook of Dyes" edited by Nobu Ogawara (1986, Kodansha), "Chemistry of Functional Dyes" edited by Nobu Okawara (1981, CMC), "Special Functional Materials" edited by Chuzaburo Ikemori (1986, 1986). The sensitizer described in CMC) can be mentioned.

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

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

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

Amine compounds include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-Ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like can be mentioned.

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

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

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

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

The content of the leveling agent is preferably 0.003 to 0.5% by weight based on 100% by weight of the coloring composition.

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

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

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

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

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

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

Commercially available products of bisphenol type epoxy resin are jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide, and D.D. E. R-331, bisphenol-A type epoxy resin such as YD-8125 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide, bisphenol-F type epoxy resin such as YDF-8170 manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd., etc. Can be mentioned.

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

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

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

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

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

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

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

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

Compounds having a monofunctional oxetane group include, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl. -3- (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3-ethylhexyloxymethyl) (Triethoxysilyl) propoxy] methyl} oxetane and the like. Examples of commercially available products include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Compounds having a bifunctional oxetane group include, for example, 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. ] Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] Methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3) -Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, Ethylglycosbis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycolbis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) -modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) -modified bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-) 3-oxetanylmethyl) ether and the like can be mentioned. Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

Compounds having a trifunctional or higher oxetane group include, for example, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl). -3-Oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaxe (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing an oxetane group (For example, the oxetane-modified phenol novolac resin described in Patent No. 3783462) and the polymer obtained by radically polymerizing a (meth) acrylic monomer such as OXE-30 described above can be mentioned.

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

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

<Curing agent, curing accelerator>
The color composition may contain a curing agent and a curing accelerator in order to assist the curing of the thermosetting resin.
Examples of the curing agent include phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine-based curing agents are preferable.
The curing accelerator is, for example, an amine compound (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N. , N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, etc.) 2-Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl- 4-Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyl, etc.) Oxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxy Ethyl-S-triazine, isocyanuric acid adduct, etc.) and the like.

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

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

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

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on 100% by weight of the total of the photopolymerization initiator and the ultraviolet absorber. Highly compatible with light sensitivity and resolution. When the coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

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

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

Commercially available products are BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", "TINUVIN 384". -2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", "TINUVIN 1130", "ADEKA STAB LA-29" manufactured by ADEKA, "RUNA-93" manufactured by Otsuka Chemical Co., Ltd. and the like.

Triazine-based organic compounds include, for example, 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol, 2- [4,6-]. Bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) Reaction product of -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidate ester, 2,4-bis "2-hydroxy-4-butoxyphenyl" -6- (2,4-dibutoxyphenyl) -1,3-5-triazine and the like.

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

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

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

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

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propanetristhioglycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetraxthiopropionate, Tris Trimercaptopropionate (2-Hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine And the like, preferably ethylene glycol bisthiopropionate, trimethylolpropanthrithiopropionate, pentaerythritol tetrakisthiopropionate and the like.

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

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

<Antioxidant>
The coloring composition of the present invention may contain an antioxidant. The antioxidant can suppress the film formed from the coloring composition from being oxidized and yellowed by a heating step such as thermosetting, and can maintain the transmittance of the film. In particular, when the colorant concentration of the photosensitive coloring composition is high, the cross-linking component is relatively small. Therefore, if measures such as using a highly sensitive cross-linking component or increasing the amount of the photopolymerization initiator are taken, yellowing of the thermal process will occur. This is to become stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

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

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

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Shinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.
Commercially available products are ADEKA's ADEKA STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320, Chemipro's KEMIOX101, 179, 76, 9425, BASF's IRGANOX1010, 1035, 1076, 1098, 1135. , 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sianox CY-1790, CY-2777 manufactured by Sun Chemical Co., Ltd. and the like.

Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} Hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.
Commercially available products are ADEKA's ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA- 402F, LA-502XP, KAMISTAB29, 62, 77, 29, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin 249 manufactured by BASF, TINUVIN111FDL, 123, 144, 292, 5100, Siasorb UV-3346, UV-3549, UV- made by Sun Chemical Co., Ltd. 3853 and the like can be mentioned.

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

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

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

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

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

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

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

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

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

Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Examples thereof include organic phosphine and phosphite. The amount of the storage stabilizer used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The amount of the adhesion improver used is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5% by weight, based on 100 parts by weight of the colorant.

<Manufacturing method of coloring composition>
The coloring composition of the present invention contains a dye, a binder resin, and a polymer (A) containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). It is preferable to produce the mixture containing the organic solvent by finely dispersing it using various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. Further, when a plurality of colorants are used, the coloring composition of the present invention can be produced by separately preparing dispersions and then mixing these dispersants. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, the above-mentioned fine dispersion step is performed. It does not have to be. When the mixture contains a pigment, it is preferable to use a dispersion aid such as a pigment derivative in combination.

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

When the colorant is dispersed in the coloring composition, a dye derivative, a dispersant (for example, a resin-type dispersant), a dispersion aid (for example, a surfactant) and the like can be appropriately used. Since the dispersion aid is excellent in dispersing the colorant and has a great effect of preventing the reaggregation of the colorant after dispersion, a color filter having high spectral transmittance can be obtained. The dye derivative is as described above.

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

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

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc. 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. , BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310. 4,320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajispar PA111, PB711, PB821, PB822, PB824 and the like manufactured by Ajisper are preferable.

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

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

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

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

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

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

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

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

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

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

<Removal of coarse particles>
The coloring composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention preferably includes a base material and a red filter segment, a green filter segment, and a blue filter segment. The color filter can also further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment. In the color filter of the present invention, at least one of a red filter segment, a green filter segment, and a yellow filter segment is preferably formed using the coloring composition of the present invention, and a green filter segment may be formed. More preferred.

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

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

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

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

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

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

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

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

If a black matrix is formed in advance before forming the filter segment on the substrate, the contrast of the display panel can be further enhanced. As the black matrix, for example, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. It is also possible to form a thin film transistor (TFT) on the transparent substrate or the reflective substrate in advance, and then form a filter segment. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the brightness can be improved.
An overcoat film or a transparent conductive film can be formed on the color filter, if necessary.

The color filter of the present invention is bonded to a facing substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by sticking it on the outside of the surface. This color liquid crystal display device is twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optical convencend bend (OCB). It can be used in the liquid crystal display mode in which colorization is performed using a color filter such as).

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

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

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

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

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

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

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

<Manufacturing of binder resin solution>
(Binder resin solution: B-1)
70.0 parts of methoxypropyl acetate was placed in a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) from the dropping tube. , 2,2'-Azobisisobutyronitrile 0.4 part mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate is added to the previously synthesized resin solution so that the non-volatile content is 40%. To prepare a binder resin solution (B-1).

(Binder resin solution: B-2 to B-4)
Binder resin solutions (B-2) to (B-4) were prepared in the same manner as in (B-1) except that the monomer composition was changed as shown in Table 1.

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

(Purple refined pigment (P-2))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. This mixture is poured into 5000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 118 parts of a purple finely divided pigment (P-2). The average primary particle size of the obtained pigment was 26.4 nm.

<Manufacturing of pigment dispersion>
(Preparation of Pigment Dispersion (PR-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition (PR-1) was prepared by filtering with the filter of.
Red fine pigment (P-1): 10.0 parts Binder resin solution (B-1): 35.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts Resin type dispersant: 15. Part 0 (20% PGMAc solution of "Ajispar PB821" manufactured by Ajinomoto Fine-Techno Co., Ltd.)

(Preparation of pigment dispersion (PV-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition (PV-1) was prepared by filtering with the filter of.
Purple fine pigment (P-2): 10.0 parts Binder resin solution (B-1): 35.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts Resin type dispersant: 15. Part 0 (20% PGMAc solution of "Ajispar PB821" manufactured by Ajinomoto Fine-Techno Co., Ltd.)

<Manufacturing of dispersant>
(Dispersant solution 1)
70 parts of methyl methacrylate, 20 parts of t-butyl methacrylate and 10 parts of methacrylic acid were charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., 6.0 parts of 1-thioglycerol was added, and the reaction was carried out for 12 hours. It was confirmed by measuring the non-volatile content that 95% had reacted. Next, 8.5 parts of pyromellitic anhydride, 115 parts of propylene glycol monomethyl ether acetate (PGMAc), and 0.20 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU) as a catalyst. Was added and reacted at 100 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The dispersant solution 1 having a non-volatile content of 50%, an acid value of 100 mgKOH / g, and a weight average molecular weight of 9,000. Got

<Manufacturing of polymer (amphoteric ion resin) having betaine structure in side chain>
Table 2 shows the structure of the ethylenically unsaturated monomer which is the precursor of the repeating unit represented by the general formula (2) used in this production example.

(Polymer J-1)
100 parts of isopropyl alcohol was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then isopropyl alcohol 50. , 65 parts of hexyl acrylate, 15 parts of N, N-dimethylaminoethyl methacrylate, 5 parts of methyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 5 parts of methacrylic acid, and 2,2'-azobisisobutyronitrile 6 A mixture of 0.0 parts was added dropwise over 2 hours, and the mixture was polymerized for 2 hours while maintaining this temperature. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of the polymer intermediate (j-1). Subsequently, 11.7 parts of 1,3-propane sultone was put into the above container, the reaction was continued at 80 ° C. for 6 hours, and the reaction was terminated when the non-volatile amine value disappeared. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and isopropyl alcohol was added to the previously synthesized resin solution so that the non-volatile content was 30%. A polymer (J-1) solution having a betaine structure in the side chain was prepared.

(Preparation of polymers J-2 to J-20)
A polymer (J-2)-(J-28) solution having a betaine structure in the side chain was obtained in the same manner as the polymer (J-1) except that the raw materials were changed to those shown in Table 3.

<Manufacturing of cationic dyes>
(Cationic dye (D-1))
C. I. Basic Blue 7 was used.
(Cationic dye (D-2))
C. I. Basic Violet 10 was used.
(Cationic dye (D-3))
C. I. Basic Red 12 was used.

The following cationic cyanine dyes are based on J. Org. Chem., 1995, 60 (8), pp 2411-2422, J. Am. Chem. Soc., 2011, 133 (40), pp 15870-15873. ..
(Manufacturing of cationic dye (D-4))
(Synthesis of intermediate d-4)
To a 100 mL 4-neck flask equipped with a thermometer, a dropping funnel and a cooling tube, 5 g of 5-chloro-2,3,3-trimethylindorenin, 5.50 g of iodomethane and 10 mL of acetonitrile were added, and the mixture was heated under reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. 40 mL of diethyl ether was added thereto, and the mixture was washed and suction filtered. 7.53 g of product was obtained. The yield was 87%. The compound was identified by a mass spectrometer (TOF-MS: autoflexII manufactured by Bruker Daltonics Co., Ltd.), and it was confirmed that the compound was the target product.

(Synthesis of D-4)
3. Add 7.53 g of intermediate (d-4) and 15 mL of acetic anhydride to a 100 mL 4-neck flask equipped with a thermometer, a dropping funnel, a cooling tube, and a nitrogen flow tube, and use the dropping funnel to add triethyl orthoformate. 83 g was added dropwise, and the mixture was heated under reflux. After 1 hour, the mixture was cooled to room temperature to precipitate a solid. The precipitated solid was suction-filtered and washed with 30 mL of ethyl acetate and 30 mL of ion-exchanged water. It was dried by heating in a hot air dryer at 40 ° C. overnight to obtain a cationic dye (D-4). The compound was identified by a mass spectrometer (TOF-MS: autoflexII manufactured by Bruker Daltonics Co., Ltd.), and it was confirmed that the compound was the target product.
(Manufacturing of cationic dyes (D-5) to (D-8))
Cationic dyes (D-5) to (D-8) were obtained using the same synthetic method as the cationic dye (D-4).

The structures of the cationic dyes (D-1) to (D-8) are shown in Table 4.

＜重合体（Ａ）を含有する染料の製造＞
（重合体（Ａ−１）を含有する染料）
側鎖にベタイン構造を有する重合体（Ｊ−１）溶液３９．０部に、ビス(トリフルオロメタンスルホニル)イミドリチウム：２．８０部（アニオン換算、前述の式（５ｃ−１）で表される構造）を添加し、メタノール１１７．０部を加え室温攪拌しこれを溶かした。ここに水７８０．０部を室温攪拌しながら６０分掛けて滴下し、滴下終了後さらに６０分室温攪拌した。次いでＣ．I．ベーシック ブルー７を４．７９部（カチオン換算、表４中の式（Ｄ−１）で表される構造）を水２２２．０部に溶解し、これを上記反応液に室温攪拌しながら６０分掛けて滴下し、滴下終了後さらに６０分室温攪拌した。反応液をろ紙に滴下して、にじみがなくなったところを終点として、共造塩化合物が得られたものと判断した。その後、吸引濾過を行い、水洗後、ろ紙上に残った共造塩化合物を乾燥機にて水分を除去して乾燥し、側鎖にベタイン構造を有する重合体（Ｊ−１）と、ビス(トリフルオロメタンスルホニル)イミドリチウムおよびベーシック ブルー７との共造塩化合物である重合体（Ａ−１）を含有する染料を得た。

<Manufacturing of dye containing polymer (A)>
(Dye containing polymer (A-1))
In 39.0 parts of a polymer (J-1) solution having a betaine structure in the side chain, 2.80 parts of bis (trifluoromethanesulfonyl) imide lithium: 2.80 parts (anion equivalent, represented by the above formula (5c-1)) Structure) was added, 117.0 parts of methanol was added, and the mixture was stirred at room temperature to dissolve it. 780.0 parts of water was added dropwise thereto over 60 minutes while stirring at room temperature, and after the completion of the dropping, the mixture was further stirred at room temperature for 60 minutes. Then C.I. I. 4.79 parts of Basic Blue 7 (cation conversion, structure represented by the formula (D-1) in Table 4) is dissolved in 222.0 parts of water, and this is dissolved in the above reaction solution in the above reaction solution at room temperature for 60 minutes. The mixture was hung and dropped, and after the dropping was completed, the mixture was further stirred at room temperature for 60 minutes. The reaction solution was dropped onto a filter paper, and it was judged that the co-produced salt compound was obtained at the end point where the bleeding disappeared. Then, suction filtration is performed, and after washing with water, the co-produced salt compound remaining on the filter paper is dried by removing water with a dryer, and the polymer (J-1) having a betaine structure in the side chain and bis ( A dye containing a polymer (A-1) which is a co-salt compound with trifluoromethanesulfonyl) imidelithium and Basic Blue 7 was obtained.

(Dyes containing polymers (A-2) to (A-65))
Hereinafter, the polymer, which is a salt-forming compound of the dye, is the same as A-1, except that the polymer having a betaine structure in the side chain, the cationic dye, and the anionic compound are changed to those shown in Table 5. A dye containing A-2) to the polymer (A-65) was produced.

<Manufacture of chloride-forming granules of cationic dye and anionic compound>
(Manufacture of dye salt-forming compound (A-66))
C. I. 4.00 parts of Basic Blue 7 (cation conversion, structure represented by the formula (D-1) in Table 4) was dissolved in 200 parts of water. Next, 2.40 parts of bis (trifluoromethanesulfonyl) imide lithium is dissolved in 100 parts of water, and the mixture is stirred at room temperature. I. The mixture was added dropwise to the aqueous solution of Basic Blue 7 over 60 minutes, and after the addition was completed, the mixture was further stirred at room temperature for 60 minutes. It was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. Then, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and C.I. I. A dye containing a dye (A-66), which is a salt-forming compound of Basic Blue 7 and bis (trifluoromethanesulfonyl) imide lithium, was obtained.
(Manufacture of dye salt-forming compound (A-67))
C. I. 4.00 parts of Basic Violet 10 (cation conversion, structure represented by the formula (D-2) in Table 4) was dissolved in 200 parts of water. Next, 2.60 parts of bis (trifluoromethanesulfonyl) imide lithium is dissolved in 100 parts of water, and the mixture is stirred at room temperature. I. The mixture was added dropwise to an aqueous solution of Basic Violet 10 over 60 minutes, and after the addition was completed, the mixture was further stirred at room temperature for 60 minutes. It was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. Then, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and C.I. I. A dye containing a dye (A-67), which is a salt-forming compound of basic violet 10 and bis (trifluoromethanesulfonyl) imide lithium, was obtained.
(Manufacture of dye salt-forming compound (A-68))
C. I. 4.00 parts of Basic Red 12 (cation conversion, structure represented by the formula (D-3) in Table 4) was dissolved in 200 parts of water. Next, 3.20 parts of bis (trifluoromethanesulfonyl) imide lithium is dissolved in 100 parts of water and stirred at room temperature. I. The mixture was added dropwise to the aqueous solution of Basic Red 12 over 60 minutes, and after the addition was completed, the mixture was further stirred at room temperature for 60 minutes. It was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. Then, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and C.I. I. A dye containing a dye (A-68), which is a salt-forming compound of Basic Red 12 and bis (trifluoromethanesulfonyl) imide lithium, was obtained.

<Manufacturing of coloring compositions for color filters>
[Example 1]
(Preparation of dye paste DP-1)
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The colored composition (DP-1) was prepared by filtering with the filter of.
Salt compound (A-1): 10.0 parts Binder resin solution (B-2): 50.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts

[Examples 2-82]
(Coloring Compositions DP-2 to DP-82)
Coloring compositions (DP-2 to DP-82) were prepared in the same manner as in Example 1 except that the salt-forming compound (A-1) and the binder resin solution (B-1) were changed to the compositions shown in Table 6. did.

[Comparative Examples 1 to 8]
(Coloring Compositions DP-83 to DP-90)
Coloring compositions (DP-83 to DP-90) were prepared in the same manner as in Example 1 except that the salt-forming compound (A-1) and the binder resin solution (B-1) were changed to the compositions shown in Table 7. did.

<Evaluation of coloring composition for color filter>
The obtained coloring composition was evaluated for brightness, coating film solvent resistance, coating film heat resistance, storage stability (viscosity), and filterability as follows. The results are shown in Tables 8 and 9. Only the evaluation of lightness was carried out by mixing with the pigment dispersion. For other evaluations, the evaluation was carried out using the coloring composition of the salt-forming compound of the produced dye alone.

(Evaluation of lightness)
Among the obtained coloring compositions, the cationic dye (D-1) was evaluated as a blue coloring material, and it was determined that x = 0.15 and y = 0.06 with a C light source (PV-1). Mixed. The cationic dyes (D-2) to (D-8) were evaluated as red colorants and mixed with (PR-1) so that x = 0.64 and y = 0.33 with a C light source. The mixed coloring composition is applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 230 ° C. for 20 minutes and allowed to cool. By doing so, a coated substrate was produced. After the heat treatment at 230 ° C., the produced coating film substrate was adjusted to have the above-mentioned chromaticity by adjusting the coating rotation speed of the spin coater. The brightness of the obtained coating film: Y value was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
When evaluated as blue ◎: Y ≧ 5.80
〇: 5.80> Y ≧ 5.65
Δ: 5.65> Y ≧ 5.60
×: 5.60> Y
When evaluated as red ◎: Y ≧ 21.8
〇: 21.8 ＞ Y ≧ 21.4
Δ: 21.4> Y ≧ 21.2
×: 21.2> Y

(Solvent resistance of coating film)
The obtained coloring composition is applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, baked in an oven at 230 ° C. for 30 minutes, and the film thickness of the coating film after heat treatment is the surface shape. Three coating substrates were prepared so that the film thickness was about 2.0 μm by measurement using a measuring device “Dektak8 (manufactured by Veeco)”. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, the coating film obtained as a chemical resistance test was immersed in 1-methyl-2-pyrrolidone for 30 minutes, and then 1-methyl-2-pyrrolidone was washed with pure water, and then the chromaticity with a C light source ( [L * (2), a * (2), b * (2)]) was measured, the color difference ΔEab * was obtained by the following formula, and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Evaluation of heat resistance of coating film)
The obtained coloring composition is applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and fired in an oven at 230 ° C. for 30 minutes to determine the surface shape of the coating film after heat treatment. Three coating substrates were prepared so that the film thickness was about 2.0 μm by measurement using a measuring device “Dektak8 (manufactured by Veeco)”. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, as a heat resistance test, the mixture was heated at 230 ° C. for 1 hour, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , Color difference ΔEab * was obtained and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Storage stability (viscosity evaluation))
The viscosities of the obtained colored composition immediately after preparation and after storage at 10 ° C. for 1 month were measured using an E-type viscometer. The ratio of (viscosity after storage for 1 month) / (viscosity immediately after adjustment) was calculated and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
⊚: Viscosity ratio is 1.00 or more and less than 1.02 〇: Viscosity ratio is 1.02 or more and less than 1.05 Δ: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 that's all

(Evaluation of filterability)
10 g of the obtained coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number; 39115221) at nitrogen pressure (0.3 MPa), and the amount obtained through the filter was measured and evaluated according to the following criteria. did.
⊚: Filtration amount is 8.0 g or more 〇: Filtration amount is 5.0 g or more and less than 8.0 g Δ: Filtration amount is 3.0 g or more and less than 5.0 g ×: Filtration amount is 3.0 g or less

As shown in Examples 1 to 63, by containing the repeating unit represented by the general formula (2) in the salt-forming compound, the polarity of the salt-forming compound is lowered, the solubility in an organic solvent is improved, and filtration is performed. The sex was very good. On the other hand, as shown in Comparative Examples 1 to 8, if the salt-forming compound does not contain the repeating unit represented by the general formula (2), the solubility in the organic solvent becomes poor and the filterability becomes poor. It was.

As shown in Examples 21 to ²² , the length of the hydrocarbon group represented by R 22 of the general formula (2) is increased, so that the solubility in the solvent is improved and the binder resin in the coloring composition is used. The compatibility was improved, and as a result, the storage stability was very good.

As shown in Examples 33 to 61, by optimizing the amount of the repeating unit represented by the general formula (2), the mobility of the salt-forming compound of the dye in the coating film during the heat treatment is lowered, and the mobility of the salt-forming compound of the dye is lowered. Heat resistance is improved by suppressing aggregation and the like.

As shown in Examples 62 to 82, the binder resin contained the repeating unit represented by the general formula (2), so that the compatibility of the entire coating film was improved and the brightness was very good. ..

In the comparative example, the results satisfying all the items were not obtained, and the effect of the present invention was proved.

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

However, when evaluating the brightness, (DP-1) and (PV-1) are mixed with a C light source so that x = 0.15 and y = 0.06, and (DP-1) and (PV-1) and (PV-) are mixed. It was prepared so that the total of 1) was 60.0 parts.

[Examples 84 to 164, Comparative Examples 9 to 16]
(Photosensitive coloring compositions (DR-2 to DR-82, DR-83 to DR-90))
The photosensitive coloring compositions (DR-2 to DR-82, DR-83 to DR-90) were prepared in the same manner as in Example 83 except that the coloring compositions were changed to the coloring compositions shown in Tables 10 and 11. Made.
However, when evaluating the brightness, the cationic dye (D-1) was evaluated as a blue color material, and x = 0.15 and y = 0.06 with a C light source (PV-1). Mixed. The cationic dyes (D-2) to (D-8) were evaluated as red colorants and mixed with (PR-1) so that x = 0.64 and y = 0.33 with a C light source.

<Evaluation of photosensitive coloring composition for color filters>
The obtained coloring composition was evaluated for brightness, coating film solvent resistance, coating film heat resistance, storage stability (viscosity), and filterability as follows. The results are shown in Tables 12 and 13. Only the evaluation of lightness was carried out by mixing with the pigment dispersion. For other evaluations, the evaluation was carried out using a photosensitive coloring composition of the salt-forming compound of the produced dye alone.

(Evaluation of lightness)
Among the obtained photosensitive coloring compositions, the cationic dye (D-1) was evaluated as a blue color material so that x = 0.15 and y = 0.06 with a C light source (PV-1). ) And mixed. The cationic dyes (D-2) to (D-8) were evaluated as red colorants and mixed with (PR-1) so that x = 0.64 and y = 0.33 with a C light source. The mixed photosensitive coloring composition is applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, dried at 70 ° C. for 20 minutes, and then the integrated light amount is 150 mJ using an ultrahigh pressure mercury lamp. The entire surface of the substrate was exposed to ultraviolet rays at / cm ^{2, and the coating film was photocured.} Then, it was heated at 230 ° C. for 20 minutes and allowed to cool to prepare a coated substrate. After the heat treatment at 230 ° C., the produced coating film substrate was adjusted to have the above-mentioned chromaticity by adjusting the coating rotation speed of the spin coater. The brightness of the obtained coating film: Y value was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
When evaluated as blue ◎: Y ≧ 5.80
〇: 5.80> Y ≧ 5.65
Δ: 5.65> Y ≧ 5.60
×: 5.60> Y
When evaluated as red ◎: Y ≧ 21.8
〇: 21.8 ＞ Y ≧ 21.4
Δ: 21.4> Y ≧ 21.2
×: 21.2> Y

(Solvent resistance of coating film)
The obtained photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, dried at 70 ° C. for 20 minutes, and then the integrated light amount was 150 mJ using an ultrahigh pressure mercury lamp. The entire surface of the substrate was exposed to ultraviolet rays at / cm ^{2, and the coating film was photocured.} Then, it was heated at 230 ° C. for 20 minutes and allowed to cool to prepare a coated substrate. The produced coating film substrate was prepared by measuring three coating substrates so that the film thickness after heat treatment at 230 ° C. was measured using a surface shape measuring device "Dektake8 (manufactured by Veeco)" and was about 2.0 μm. Made. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, the coating film obtained as a chemical resistance test was immersed in 1-methyl-2-pyrrolidone for 30 minutes, and then 1-methyl-2-pyrrolidone was washed with pure water, and then the chromaticity with a C light source ( [L * (2), a * (2), b * (2)]) was measured, the color difference ΔEab * was obtained by the following formula, and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Evaluation of heat resistance of coating film)
The obtained photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, dried at 70 ° C. for 20 minutes, and then the integrated light amount was 150 mJ using an ultrahigh pressure mercury lamp. The entire surface of the substrate was exposed to ultraviolet rays at / cm ^{2, and the coating film was photocured.} Then, it was heated at 230 ° C. for 20 minutes and allowed to cool to prepare a coated substrate. The produced coating film substrate was prepared by measuring three coating substrates so that the film thickness after heat treatment at 230 ° C. was measured using a surface shape measuring device "Dektake8 (manufactured by Veeco)" and was about 2.0 μm. Made. The obtained photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, dried at 70 ° C. for 20 minutes, and then the integrated light amount was 150 mJ using an ultrahigh pressure mercury lamp. The entire surface of the substrate was exposed to ultraviolet rays at / cm ^{2, and the coating film was photocured.} Then, it was heated at 230 ° C. for 20 minutes and allowed to cool to prepare a coated substrate. The produced coating film substrate was prepared by measuring three coating substrates so that the film thickness after heat treatment at 230 ° C. was measured using a surface shape measuring device "Dektake8 (manufactured by Veeco)" and was about 2.0 μm. Made. Use a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, as a heat resistance test, the mixture was heated at 230 ° C. for 1 hour, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , Color difference ΔEab * was obtained and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Storage stability (viscosity evaluation))
The viscosities of the obtained photosensitive coloring composition immediately after preparation and after storage at 10 ° C. for 1 month were measured using an E-type viscometer. The ratio of (viscosity after storage for 1 month) / (viscosity immediately after adjustment) was calculated and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
⊚: Viscosity ratio is 1.00 or more and less than 1.02 〇: Viscosity ratio is 1.02 or more and less than 1.05 Δ: Viscosity ratio is 1.05 or more and less than 1.10 ×: Viscosity ratio is 1.10 that's all

(Evaluation of filterability)
10 g of the obtained photosensitive coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number; 39115221) under a nitrogen pressure (0.3 MPa), and the amount obtained through the filter was measured. Evaluated in.
⊚: Filtration amount is 8.0 g or more 〇: Filtration amount is 5.0 g or more and less than 8.0 g Δ: Filtration amount is 3.0 g or more and less than 5.0 g ×: Filtration amount is 3.0 g or less

The results of the photosensitive coloring composition were similar to those of the coloring compositions shown in Examples 1 to 82 and Comparative Examples 1 to 8.

<Making color filters>
By using the photosensitive coloring composition of the present invention, a color filter exhibiting good performance could be produced.

Claims (6)

A coloring composition for a color filter containing a colorant, a binder resin, and an organic solvent.
The colorant is characterized by containing a dye containing a polymer (A) containing at least a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). Coloring composition for color filters.

General formula (1)

[In general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² and R ¹³ each independently represent a divalent linking group, and X ⁺ represents a divalent cationic linking group. Y ⁻ represents a monovalent anionic group. B ⁺ is a cation derived from a cationic dye, and Z ⁻ represents an anion derived from an anionic compound. However, the cationic dye is at least one selected from the group consisting of xanthene dyes, triphenylmethane dyes, and cyanine dyes. ]

General formula (2)

[In the general formula (2), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a linear, branched, or cyclic hydrocarbon group having 6 or more carbon atoms. ] The coloring composition for a color filter according to claim 1, wherein the hydrocarbon group has 10 or more carbon atoms in the general formula (2). When the weight of the polymer (A) of the polymer (A) excluding the cation represented by ^{B + and the anion represented by Z −} in the general formula (1) is 100% by weight. The coloring composition for a color filter according to claim 1 or 2, wherein the content of the repeating unit represented by the general formula (2) is 10 to 50% by weight. The coloring composition for a color filter according to any one of claims 1 to 3, wherein the binder resin contains a repeating unit represented by the general formula (2). The coloring composition for a color filter according to any one of claims 1 to 4, further containing a photopolymerizable monomer and / or a photopolymerization initiator. A color filter formed by the coloring composition for a color filter according to any one of claims 1 to 5.