JP6340871B2 - Coloring composition for color filter, and color filter - Google Patents

Description

  The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

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

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

  In order to solve the above-described problems, a technique has been proposed in which a dye, not a pigment, is dissolved as a colorant in a resin or the like (see, for example, Patent Documents 1 and 2). By using the dye, there is an advantage that the contrast ratio can be improved because the lightness can not be achieved by the pigment and the light scattering can be suppressed because it is not the particle. However, dyes generally have poor solubility in organic solvents, and because they are fragile pigment skeletons, they are extremely deficient in heat resistance and light resistance, so that they are difficult to put into practical use because there are many problems as coloring compositions for color filters.

  In particular, yellow dyes generally have poor heat resistance and light resistance, and solid dyes cannot be used because they do not dissolve in organic solvents. Therefore, a technique for imparting resistance by reacting a basic yellow dye and a sulfonic acid compound has been proposed. (For example, refer to Patent Document 3). However, the yellow dye cannot sufficiently bring out optical performance such as brightness and contrast ratio. Accordingly, there is a need for a high-quality color filter that has excellent brightness, excellent durability, and a higher contrast ratio.

JP-A-2-127602 JP-A-6-75375 JP 2013-47285 A

  The objective of this invention is providing the coloring composition for color filters excellent in the brightness, heat resistance, and contrast ratio, and a color filter.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a color filter containing a salt-forming compound (general formula 1) obtained by reacting an imido acid anion with a cationic dye. Coloring composition has high brightness and high heat resistance. It has been found that it has a high contrast ratio, and the present invention has been made based on this finding.

That is, the present invention is a color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, and the colorant is represented by the following general formula (1): It is related with the coloring composition for color filters characterized by being a salt formation compound of these.
General formula (1)
[In General Formula (1), D ⁺ represents a cationic dye having a maximum absorption wavelength of 360 nm to 500 nm, R ¹ represents an aliphatic hydrocarbon group which may have a substituent, and R ² represents a fluorine atom. Is an aromatic hydrocarbon group . ]

In the present invention, the cationic dye may be at least one selected from the group consisting of methine dyes, azo dyes, auramine dyes, acridine dyes, cetoflavin dyes, coumarin dyes, and azomethine dyes. It related to the color filter for coloring composition comprising a cationic dye dyes.

In addition, the present invention relates to the coloring composition for a color filter, wherein in the general formula (1), R ¹ is a trifluoromethyl group and R ² is a pentafluorophenyl group.

Moreover, this invention relates to the said coloring composition for color filters which contains an organic dye and / or an organic pigment further.
About.

Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

Furthermore, the present invention relates to a color filter comprising a filter segment formed from the colored composition for a color filter on a substrate.

The present invention is a color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, and a salt-forming compound of a specific imidic acid anion of the present application and a specific cationic dye of the present application is used as the colorant. Thus, a color filter coloring composition having high brightness, high heat resistance, and a high contrast ratio can be obtained.

Hereinafter, the present invention will be described in detail. Further, “CI” in this specification means a color index (CI).

<Colorant>
The coloring composition for a color filter of the present invention contains a salt-forming compound obtained by reacting an imidoic acid anion described below with a specific cationic dye of the present application, so that it has high brightness, high heat resistance, and higher contrast. It has an excellent effect of having a ratio. It is also preferable to use a pigment or dye in combination.

[Salt-forming compound represented by general formula (1)]
The salt-forming compound represented by the general formula (1) of the present invention is a salt of the imido acid anion represented by the general formula (7) and the cationic dye represented by the general formulas (2) to (8). It can be obtained by forming.

General formula (1)
[In General Formula (1), D + represents a cationic dye having a maximum absorption wavelength of 360 nm to 500 nm, and R ¹ and R ² are each independently a hydrocarbon group which may have a substituent, or The heterocyclic group which may have a substituent is represented. R ¹ and R ² do not show the same structure. ]

(Imidate anion represented by the general formula (7))
General formula (7)

[R ¹ and R ² in General Formula (7) are synonymous with R ¹ and R ² in General Formula (1). ]

In the general formula (1), examples of the “hydrocarbon group” include “aliphatic hydrocarbon group”, “alicyclic hydrocarbon group”, “aromatic hydrocarbon group”, and the like.
Examples of the “aliphatic hydrocarbon group” include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, pentadecyl group, hexadecyl group Linear alkyl groups such as a group, octadecyl group, nonadecyl group and pentadecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and isooctyl group; and the like.
Examples of the “alicyclic hydrocarbon group” include cycloalkyl groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group.
Examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenyl group, a naphthyl group, and the like.

In the general formula (1), examples of the “heterocyclic group” include indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, quinoline And a ring.

  In the general formula (1), examples of the “substituent” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, Aliphatic hydrocarbon groups such as neopentyl group and tert-pentyl group; polymerizable functional groups such as (meth) acryloyl group, vinylaryl group, vinyloxy group, allyl group and epoxy group; phenyl group, o-tolyl group, m- Aromatic hydrocarbon groups such as tolyl, p-tolyl, xylyl, mesityl, o-cumenyl, m-cumenyl, p-cumenyl; methoxy, ethoxy, propoxy, isopropoxy, butoxy Group, isobutoxy group, sec-butoxy group, tert-butoxy group, alkoxy group such as pentyloxy group; phenoxy Aryloxy groups such as benzyloxy groups; aralkyloxy groups such as benzyloxy groups; groups having an ester bond such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group; methylsulfamoyl group, dimethylsulfa group Moyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfa Alkylsulfamoyl groups such as moyl group and di-n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butyls Honiru group, tert- alkylsulfonyl group such as butyl sulfonyl group; can be nitro group, a cyano group and the like; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom.

The R ¹ in the general formula (1), in the well, Ri aliphatic hydrocarbon radical der may have a substituent, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which is substituted with a fluorine atom It is preferable that it is a trifluoromethyl group.

Among the above, R ^{2 in the} general formula (1) is more preferably an aromatic hydrocarbon group substituted with a fluorine atom from the viewpoint of improving solubility, and a p-fluorophenyl group or a pentafluorophenyl group. More preferably it is.

Specific examples of the imido acid anion include the following imido acid anions, but the present invention is not limited thereto. Moreover, n shows the integers 1-5. In addition, as for the counter of the imido acid anion (IC-1 to IC-50) shown below, Na ^<+> , K ^<+> , tetrabutylammonium, trimethylammonium, etc. are mentioned.

(Cationic dye)
The cationic dye of the present application is not particularly limited as long as the maximum absorption wavelength is a cation having a maximum absorption wavelength of 360 nm to 500 nm. For example, methine dyes, azo dyes, auramine dyes, acridine dyes, Examples include cetoflavin dyes, coumarin dyes, and azomethine dyes, which can be preferably used.

{Metin dyes}
A methine dye is a dye having a methine group (—CH═) linked by a conjugated double bond in the molecular structure. As the methine dye, those represented by the following general formula (2) are preferable.
[In general formula (2),
X represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ^{3 to} R ⁶ are each independently a hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted Represents a substituted aryl group or a substituted or unsubstituted acyl group;
R ⁷ represents a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁸ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group,
A represents —CH═CH—, —CH═CH—NR ⁹ —,
R ⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

R ⁸ is preferably a group represented by the following general formulas (2a) to (2g).

[In the general formulas (2a) to (2g)
R ¹⁰ and R ¹¹ each independently represent a C 1-6 alkyl group,
R ^{12 to} R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a nitro group. ]

Specific examples of the general formula (2) include the following cationic dyes, but the present invention is not limited thereto. Incidentally, the counter of cationic dye shown below ^{are, Cl -, Br -, I} - Moshiku _CH 3 SO ₄ ^-, and the like.

{Azo dyes}
An azo dye is a dye having an azo group in the dye structure and always having an aromatic nucleus on one side. As the azo dye, those represented by the following general formulas (3-1) to (3-3) are preferable.

[In the general formulas (3-1) to (3-3),
R ¹⁹ , R ²⁰ and R ²⁶ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ²¹ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group,
X represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ^{22 to} R ²⁵ and R ²⁷ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group,
R ²⁸ represents a group forming a quaternary ammonium salt. ]

Examples of the _{^{R 28, -NR 29 C m H}} 2m N + R 30 R 31 R 32 (m is an integer from 1 to ^{5, R 29} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^{30 to} R ³² each independently represents an alkyl group having 1 to 6 carbon atoms), —COC _m H _2m N ⁺ R ³⁰ R ³¹ R ³² (m, R ³⁰ , R ³¹ and R ³² are as defined above). in _{a), - C m H 2m N} + (NH 2) is ^R 33 ^{R 34} (m are as defined ^{above, R 33} and ^{R 34,} independently of one another, represent an alkyl group having 1 to 6 carbon atoms ) Is preferred.

R ²¹ is preferably a group represented by the following general formulas (3a) to (3e).

[In the general formulas (3a) to (3e)
R ³⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group,
R ³⁶ and R ³⁷ each independently represent an alkyl group having 1 to 6 carbon atoms,
R ³⁸ and R ⁴³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³⁹ , R ⁴¹ , R ⁴⁴ , and R ⁴⁵ each independently represent a hydrogen atom and 1 to 6 carbon atoms. Represents an alkyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a cyano group;
R ⁴⁰ and R ⁴² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group. ]

Specific examples of the general formula (3) include the following cationic dyes, but the present invention is not limited thereto. Incidentally, the counter of cationic dye shown below ^{are, Cl -, Br -, I} - Moshiku _CH 3 SO ₄ ^-, and the like.

{Auramine dye}
As an auramine type | system | group pigment | dye, what is represented by following General formula (4) is preferable.
[In general formula (4),
R ^{46 to} R ⁵¹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have a substituent,
R ⁵² and R ⁵³ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms. ]

Specific examples of the general formula (4) include the following cationic dyes, but the present invention is not limited thereto. Incidentally, the counter of cationic dye shown below ^{are, Cl -, Br -, I} - Moshiku _CH 3 SO ₄ ^-, and the like.

{Acridine dyes}
As the acridine dye, those represented by the following general formula (5) are preferable.

[In general formula (5),
R ^{54 to} R ⁵⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have a substituent,
R ⁵⁹ , R ⁶⁰ and R ⁶¹ each independently represent a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 6 carbon atoms. ]

Specific examples of the general formula (5) include the following cationic dyes, but the present invention is not limited thereto. Incidentally, the counter of cationic dye shown below ^{are, Cl -, Br -, I} - Moshiku _CH 3 SO ₄ ^-, and the like.

{Cetoflavin dye}
As the cetoflavin dye, those represented by the following general formula (6) are preferable.

[In general formula (6),
Z represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ⁶² and R ⁶⁴ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁶³ , R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. ]

Specific examples of the general formula (6) include the following cationic dyes, but the present invention is not limited thereto. Incidentally, the counter of cationic dye shown below ^{are, Cl -, Br -, I} - Moshiku _CH 3 SO ₄ ^-, and the like.

{Coumarin dyes}
As a coumarin type | system | group pigment | dye, what is represented by following General formula (7) is preferable.

[In general formula (7),
R ⁶⁷ represents a group that forms a quaternary ammonium salt;
R ⁶⁸ and R ⁶⁹ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms,
R ⁷⁰ and R ⁷¹ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms.
R ⁶⁸ and R ⁷⁰ , R ⁶⁹ and R ⁷¹ can each independently form an aliphatic saturated hydrocarbon or aromatic cyclic structure. ]

R ⁶⁷ is preferably a group represented by the following general formulas (7a) to (7b).

[In the general formulas (7a) and (7b)
L represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
Each of R ⁷² independently represents a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms;
R ⁷³ and R ⁷⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. ]

Specific examples of the general formula (7) include the following cationic dyes, but the present invention is not limited thereto. Incidentally, the counter of cationic dye shown below ^{are, Cl -, Br -, I} - Moshiku _CH 3 SO ₄ ^-, and the like.

{Azomethine dyes}
An azomethine dye is a dye having an azomethine group (—C═N) linked by a conjugated double bond in its intramolecular structure. As the azomethine dye, those represented by the following general formula (8) are preferable.

[In general formula (8),
X represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ^{75 to} R ⁷⁸ are each independently a hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted Represents a substituted aryl group or a substituted or unsubstituted acyl group;
R ⁷⁹ represents a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁸⁰ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group,
A is, -CH = N -, - CH = N-NR 81 - represents,
R ⁸¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

R ⁸⁰ is preferably a group represented by the following general formulas (8a) to (8g).

[In the general formulas (8a) to (8g),
R ⁸² and R ⁸³ each independently represent an alkyl group having 1 to 6 carbon atoms,
R < ⁸⁴ > -R < ⁹⁰ > represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, and a nitro group mutually independently. ]

Specific examples of the general formula (8) include the following cationic dyes, but the present invention is not limited thereto. Incidentally, the counter of cationic dye shown below ^{are, Cl -, Br -, I} - Moshiku _CH 3 SO ₄ ^-, and the like.

General formula (2), (2a)-(2g), (3-1)-(3-3), (3a)-(3e), (4), (5), (6), (7), (7a) to (7b), (8), (8a) to (8g)
Examples of the “alkyl group” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the “alkoxy group” include methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and the like.
As the “aryl group”, a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a tannaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group , Indacenyl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group , Triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, Kisaseniru group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, ovalenyl group and the like,
Examples of the “halogen atom” include fluorine, chlorine, bromine and iodine.
Examples of the “acyl group” include acetyl group, ethanoyl group, propanoyl group, isopropanoyl group, butanoyl group, isobutanoyl group, sec-butanoyl group, tert-butanoyl group and the like.
Examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group, a naphthyl group, and the like.
Examples of the “heterocyclic group” include indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, quinoline ring, and the like.

Moreover, general formula (2), (2a)-(2g), (3-1)-(3-3), (3a)-(3e), (4), (5), (6), (7 ), (7a)-(7b), (8), (8a)-(8g)
“Organic group having a polymerizable functional group” is a group composed of an atomic group that contains a polymerizable functional group, contains a carbon-hydrogen bond as a whole, and may contain atoms other than carbon if necessary. Indicates. Specifically, there are a case where it consists of only a polymerizable functional group and a case where it contains a polymerizable functional group and a linking group.
Here, examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group, an epoxy group, an isocyanate group, and the like (as viewed from the cyanine skeleton), an alkylene group (hereinafter referred to as -X- and -XO- group, -XNH- group, arylene group, aryleneoxy group, -XCONH- group, -XCOO- group, -XOCO- group, -XCOOX- group, -XOCOXX- group, -XCOOXCOO- group , -XOCOXCOO- group, and the like.

General formula (2), (2a)-(2g), (3-1)-(3-3), (3a)-(3e), (4), (5), (6), (7), (7a) to (7b), (8), (8a) to (8g)
Examples of the “substituent” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and tert-pentyl group. Aliphatic hydrocarbon groups such as; polymerizable functional groups such as (meth) acryloyl groups, vinylaryl groups, vinyloxy groups, allyl groups, epoxy groups; phenyl groups, o-tolyl groups, m-tolyl groups, p-tolyl groups , Xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group and other aromatic hydrocarbon groups; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec- Alkoxy groups such as butoxy group, tert-butoxy group and pentyloxy group; aryloxy groups such as phenoxy group An aralkyloxy group such as a benzyloxy group; a group having an ester bond such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetoxy group, or a benzoyloxy group; a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfuryl group; Famoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfamoyl group, di- alkylsulfamoyl groups such as n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert- Alkylsulfonyl groups such as Chirusuruhoniru group; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom; a nitro group, can be a cyano group.

(Salt formation)
The salt-forming compound of the present invention stirs or vibrates an aqueous solution in which an imido acid anion and a cationic dye are dissolved, or mixes an aqueous solution of an imido acid anion and an aqueous solution of a cationic dye under stirring or vibration. Thus, the salt-forming compound can be easily obtained. In the aqueous solution, the anionic group of the imido acid anion and the cationic group of the cationic dye are ionized, and these are ionically bonded, the ion-bonded portion becomes insoluble in water, and the salt-forming compound is precipitated. On the contrary, a salt composed of a counter cation of an imido acid anion and a counter anion of a cationic dye is water-soluble and can be removed by washing with water. As the imido acid anion and the cationic dye to be used, only a single kind or a plurality of kinds having different structures may be used.
When the cationic dye or imido acid anion is insoluble in water, each is appropriately dissolved in a soluble solvent, heated and stirred, and then the solvent is distilled off under reduced pressure or normal pressure. A salt-forming compound may be obtained by removing a salt as a by-product by adding water to the product and reslurry to remove the salt as a by-product, followed by filtration by filtration. At this time, as a solvent to be used, a water-soluble organic solvent described later can be used.

  The salt-forming compound of the present invention is preferably a salt-forming compound obtained by removing a salt composed of a counter cation of an imido acid anion and a counter anion of a cationic dye. When a by-product (for example, NaCl) generated by salt formation exists in the salt-forming compound, the salt-forming compound may precipitate over time in the colored composition.

  As an aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the imido acid anion and the cationic dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N, N -Dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, 4- And methoxy-4-methylpentanone. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight (100% by weight) of the aqueous solution.

  The ratio of the imidic acid anion to the cationic cyanine dye is such that the molar ratio of the anionic unit of the imidic acid anion to the total cationic groups of the cationic dye is in the range of 10/1 to 1/4. The salt compound can be suitably adjusted, and the range of 2/1 to 1/2 is more preferable.

<Other colorants that can be used in combination>
The colorant can be used in combination with a pigment or another dye.
When used in combination with other colorants, it is preferable to use organic pigments in order to adjust the hue and improve resistance. When the salt-forming compound of the present invention and the organic pigment are used in combination, the use ratio of the salt-forming compound of the present invention and the organic pigment is 1 to 80 parts by weight of the salt-forming compound of the present invention with respect to 100 parts by weight of the organic pigment. Preferably there is. More preferably, it is 5 to 60 parts by weight. When the addition amount of the salt-forming compound of the present invention is within this range, a composition excellent in hue and reproducible chromaticity region can also be obtained.

[Organic pigments]
As the organic pigment used in combination, the following are used for each color filter segment. These pigments can be used alone or in admixture of two or more at any ratio as required.

(Pigment forming red filter segment)
As the red pigment forming the red filter segment, the red pigment or red dye described below can be used in combination.
Examples of red pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, the diketopyrrolopyrrole pigment described in JP-T-2011-523433, or JP2013-161025A Although the naphthol azo pigment etc. which are described in gazette are mentioned, it is not limited to these. Among these, C.I. I. Pigment Red 177, 242, 254, and 269 are preferably used.
In order to form a red filter segment, a yellow or orange pigment may be used in combination. Examples of yellow or orange pigments include yellow pigments and orange pigments described below.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the quinophthalone pigment described in Japanese Patent No. 4993026 is used, but is not particularly limited thereto. . Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 71, 73 or the like is used.

(Pigment forming blue filter segment)
Examples of the pigment forming the blue filter segment include blue pigments such as C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 and the like. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination, but are not particularly limited thereto.
Among these, from the viewpoint of brightness and contrast ratio, C.I. I. Pigment Blue 15: 1, 15: 6 is particularly desirable.

(Pigment forming green filter segment)
Examples of the pigment forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37, 58, zinc phthalocyanine pigment described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, etc. Although the aluminum phthalocyanine pigment of description is mentioned, it is not specifically limited to these.
Among these, C.I. I. Pigment Green 36, 58 and aluminum phthalocyanine pigment are preferably used.
In addition, a yellow pigment can be used in combination with the green coloring composition in order to adjust the hue. Among them, 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, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 and the quinophthalone pigment described in Japanese Patent No. 4993026 can be used in combination. In particular, it is not limited to these.
Among these, C.I. I. Pigment Yellow 138, 150 or the like is preferably used.

  In the coloring composition for a color filter of the present invention, the concentration of the coloring agent with respect to all the non-volatile components is preferably 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of obtaining sufficient color reproducibility. Most preferably, it is 20 to 80% by weight. When the concentration of the colorant component is less than 10% by weight, sufficient color reproducibility may not be obtained. When the concentration exceeds 90% by weight, the concentration of the colorant carrier such as a binder resin is lowered, and the color composition May become unstable.

(Miniaturization of pigment)
The pigment that can be used in the present invention is preferably used after being refined, but the refinement method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As illustrated, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed.

  The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using 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 sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

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

[Organic dyes]
Next, the organic dye that can be used in combination with the salt-forming compound of the present invention will be described. Examples of the dyes that can be used in combination include compounds classified as dyes by the Color Index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (Color Dyeing Co., Ltd.). Oil-soluble dyes, acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, mordant dyes, and the like. Of these, oil-soluble dyes, acid dyes, metal complex dyes, and basic dyes are preferred.
Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes.

(Oil-soluble dye)
When an oil-soluble dye is used, a phthalocyanine dye, a xanthene dye, or an anthraquinone dye is preferable from the viewpoint of lightness.
Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, or C.
I. Solvent violet 10 etc. are mentioned.

  Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.

  Examples of anthraquinone oil-soluble dyes include CI Solvent Red 172, 222, CI Solvent Violet 60, and the like.

(Acid dyes)
Examples of triarylmethane acid dyes include CI Acid Blue 1, 3, 5, 7, 9, 11, 15, 17, 19, 22, 24, 38, 48, 75, 83, 90, 91, 93. 93: 1, 100, 103, 104, 109, 110, 119, 147, 269, 123, 213, CI Direct Blue 41, CI Acid Violet 17, 19, 21, 23, 25, 38 49, 72, direct blue 41, and the like.

Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

  As an anthraquinone acid dye, CI Acid Blue 23, 25, 27, 35, 40, 41, 43, 45, 47, 49, 51, 53, 55, 56, 62, 68, 69, 78, 80 81: 1, 11, 124, 127, 127: 1, 140, 150, 175, 215, 230, 277, 344, CI Acid Violet 41, 42, 43, CI Acid Green 25, 27 Or direct violet 17 and the like.

Examples of azo acid dyes include CI Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108. 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337;
CI Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127;
CI Acid Violet 11, 56, 58;
CI Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151;
CI Acid Brown 2, 4, 13, 248;
CI Acid Blue 92, 102, 113, 117 and the like.

(Basic dye)
When a basic dye is used, a triarylmethane dye, a methine dye, or a xanthene dye is preferable from the viewpoint of lightness.
Examples of the triarylmethane basic dye include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like. Among them, C.I. I. It is preferable to use Basic Blue 7, Green 4, Green 1, and Violet 3.

  Examples of methine basic dyes include C.I. I. Basic Red 12, 13, 13 (Astrazon Brilliant Red 4G), 15, 27 (Maxilon Pink B), 28, 37, 52, 90 (Brilliant Red 5G), C.I. I. Basic Violet 7 (Astrazon Red 6B). Among them, C.I. I. Basic Red 12 is preferably used.

Examples of rhodamine-based basic dyes include C.I. I. Basic Red 1 (Rhodamine 6G, 6GCP), 3 and 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among them, C.I. I. Basic Red 1, Violet 10 and Violet 11 are preferably used.

Examples of flavin basic dyes include C.I. I. Basic Yellow 1,
Examples of auramine basic dyes include C.I. I. Basic Yellow 2, 3,
Examples of the safranine basic dye include C.I. I. Basic Red 2,
Examples of the acridine basic dye include C.I. I. Basic Yellow 5,
Examples of the oxazine-based basic dye include C.I. I. Basic Blue 3,
Examples of thiazine-based basic dyes include C.I. I. Basic Blue 24,
Examples of methylene blue basic dyes include C.I. I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), 25 (Basic Blue GO), 24 (New Methylene Blue NX) and the like. Among them, C.I. I. Basic Yellow 1, Blue 9, Blue 24 and Blue 25 are preferably used.

  Examples of azo basic dyes include Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16, Basic Brown 17, and the like.

(Metal complex dyes)
Since the metal complex dye exhibits a fluorescence quenching effect with respect to a dye having fluorescence, it can be suitably used in the present invention.
Examples of the metal complex dye include C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161, C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99, C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; I. Solvent Blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid Red 211 is exemplified. Among these, from the viewpoint of fluorescence quenching, C.I. I. Solvent Yellow 21, 79, 81, 82, C.I. I. Solvent Orange 41, 54, 56, 62, 99, C.I. I. Solvent red 8, 118, 122, 127 are preferred. These metal complex dyes may be used alone or in combination of two or more.

<Binder resin>
The binder resin is one that disperses a colorant, particularly a salt-forming compound and a pigment, or one that dyes and permeates the salt-forming compound, and examples thereof include a thermoplastic resin. In the present invention, the colorant is composed of the salt-forming compound or the salt-forming compound and a pigment.

  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. Moreover, when using with the form of an alkali image development type color resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  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 resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

  The molecular weight of the binder resin used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 5,000 to 100,000. More preferably, it is 7,000-50,000. It is preferable that the converted weight average molecular weight of the binder resin is 5,000 to 100,000, because film loss is unlikely to occur during development, and the non-pixel portion is liable to be easily removed during development. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  When the binder resin is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and an aromatic group The balance of groups is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The binder resin is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances will be insufficient, and if it is more than 500 parts by weight, the concentration of the colorant will be low and color characteristics may not be exhibited.

<Thermosetting compound>
In the present invention, it is preferable to further include a thermosetting compound in combination with the thermoplastic resin which is a binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by including a thermosetting compound, it reacts at the time of firing the filter segment to increase the crosslinking density of the coating film, so that the heat resistance of the filter segment is increased. This improves the effect of suppressing pigment aggregation during firing of the filter segment and improving the contrast ratio.

  Examples of thermosetting compounds include epoxy 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, melamine compounds and / or resins, Examples include urea compounds and / or resins, and phenol compounds and / or resins, but the present invention is not limited thereto. In the coloring composition for a color filter of the present invention, an epoxy compound and / or a resin are preferably used.

The epoxy compound may be a low molecular compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Polyphenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimene) Methanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, alcohols Etc. glycidylated Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine-based epoxy resin, glycidyl ester type epoxy resins, but are not limited to these would normally epoxy compound used. These may be used alone or in combination of two or more.

  As a commercial item, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more) Is a trade name; manufactured by Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name) ; Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (Product Name; Japan Epoxy Resin Co., Ltd.), EPPN-201 (Product Name; Nippon Kayaku Co., Ltd.), JER152, JER154 Name: Japan Epoxy Resin Co., Ltd. , EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (above are trade names: manufactured by Daicel Chemical Industries, Ltd.) , Denacol EX-810, EX-830, EX-851, EX-512, EX-421, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation) However, it is not limited to these.

  The compounding amount of the epoxy compound is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 0.5 part by weight, the effect of improving heat resistance is small. If the amount is more than 300 parts by weight, a problem may occur when forming a filter segment by photolithography.

  Moreover, in order to assist hardening of a thermosetting compound, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited, and can react with thermosetting compounds. Any curing agent may be used as long as it is. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting compounds.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate the formation.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, since the salt-forming compound used in the present invention and the optional pigment are well dispersed and dissolved, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and 3-methoxybutanol, and ketones such as cyclohexanone. In particular, it is most preferable to use 3-methoxybutanol from the viewpoint of solubility in a salt-forming compound.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. In the case of using two or more kinds of mixed solvents, it is preferable that the above-mentioned preferable organic solvent is contained in an amount of 65 to 95% by weight.

  In addition, 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 colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Dispersion>
When the coloring composition of the present invention further contains a pigment in a colorant carrier composed of a salt-forming compound, the binder resin and a solvent, it is preferably combined with a dispersing aid such as a dye derivative or a resin-type dispersant. It can be produced by finely dispersing using various dispersing means such as a present roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other colorants and the like separately dispersed in a colorant carrier.

[Dispersion aid]
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the salt-forming compound is also expected to play a role as a pigment dispersion aid.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

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

  The resin-type dispersant has a pigment-affinity part that has the property of adsorbing to the additive pigment and a part that is compatible with the colorant carrier, and adsorbs to the additive pigment to stabilize dispersion in the colorant carrier. It works. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

   Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, 21116 or LACTIMON, LACTIMON-WS or BYKUMEN, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940 manufactured by Nippon Lubrizol Co., Ltd. 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 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, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The amount of the resin-type dispersant and surfactant added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the added pigment (100% by weight). It is. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Photopolymerizable monomer>
The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

  The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

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 ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable monomers can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds An imidazole compound; or a titanocene compound.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Non, 4,4′-diethylaminobenzophenone and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

 More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the weight (100% by weight) of the total solid content of the color filter coloring composition. . If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.
The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  These antioxidants can be used singly or in combination of two or more at any ratio as required. When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, 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-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Removal of coarse particles>
The coloring composition of the present invention is mixed with 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 by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. 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 this invention comprises the filter segment formed using the coloring composition for color filters of this invention. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment, or those having a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

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

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”.

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

(Resin weight average molecular weight (Mw), number average molecular weight (Mn))
Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

<Binder resin production method>
(Preparation of binder resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The binder resin solution 1 was prepared by adding. The weight average molecular weight (Mw) was 26000.

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of binder resin solution 3)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device, heated to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 1.33 of 2,2′-azobisisobutyronitrile Part of the mixture was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.
Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, after cooling to room temperature, 6.5 parts of 2-methacryloyloxyl ethyl isocyanate, A mixture of 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours.
About 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin solution 4)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100 mol% of glycidyl group), and 120 ° C. Then, the reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain a copolymer solution.
Further, 19.5 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a binder resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Production method of fine pigment>
(Blue refined pigment (P-1): PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “Lionol Blue ES”) 100 parts, 800 parts of ground salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. did. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Purple refined pigment (P-2): PV23)
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts purple refinement | purification pigment (P-2). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Red fine pigment (P-3): PR254)
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 ("IRGAZIN RED 2030" manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Red fine pigment (P-4): PR177)
Anthraquinone red pigment C.I. I. 120 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-4). The average primary particle diameter of the obtained pigment was 38.9 nm.

(Green refined pigment (P-5): PG36)
Phthalocyanine green pigment C.I. I. 120 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of green refined pigment (P-5). The average primary particle diameter of the obtained pigment was 32.6 nm.

(Green fine pigment (P-6): PG58)
Phthalocyanine green pigment C.I. I. 120 parts of Pigment Green 58 (“Fastgen Green A110” manufactured by DIC Corporation), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of green refined pigments (P-6). The average primary particle diameter of the obtained pigment was 32.6 nm.

(Blue refined pigment (P-7): Aluminum phthalocyanine pigment)
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (53).

  Subsequently, 100 parts of the aluminum phthalocyanine pigment represented by the formula (53), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. . The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. A fine pigment (P-7 intermediate) was obtained. The average primary particle size was 30.4 nm.

Formula (53)

Subsequently, 100 parts of aluminum phthalocyanine pigment represented by the formula (53) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. . After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (54).
The obtained aluminum phthalocyanine pigment represented by the formula (54) was subjected to a salt milling treatment similar to that for the blue fine pigment (P-7 intermediate) to obtain a blue fine pigment (P-7). The average primary particle size was 31.2 nm.

Formula (54)

<Method for producing pigment paste>
(Preparation of pigment paste PP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed 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. A colored composition (PP-1) was produced by filtration using a filter.
Finer pigment (P-1): 10.0 parts Binder resin solution 1: 35.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts Resin-type dispersant: 15.0 parts (Ajinomoto Fine (20% PGMAc solution of “Ajisper PB821” manufactured by Techno)

(Preparation of pigment paste PP-2-7)
Pigment pastes (PP-2 to 7) were obtained in the same manner as the pigment paste (PP-1) except that the type of fine pigment described in Table 1 was changed.

(Preparation of pigment paste PP-8)
The following mixture was stirred and mixed so as to be uniform, and then dispersed 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. A colored composition (PP-8) was produced by filtration using a filter.
Refined pigment (P-3): 7.0 parts Refined pigment (P-4): 7.0 parts Binder resin solution 1: 35.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 Parts Resin-type dispersant: 15.0 parts (20% PGMAc solution of “Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.)

<Cationic dye>
The cationic dyes listed in Tables 2 to 4 are manufactured by Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co.

<The manufacturing method of the imido acid anion shown by General formula (1)>
(Synthesis of imido acid anion G-1)

To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube was added 3.58 g (1.1 equivalents) of trifluoromethanesulfonamide, 5.53 g (2 equivalents) of potassium carbonate, and 60 ml of acetonitrile. Then, 3.53 g of pentafluorobenzenesulfonyl chloride was added in portions, and the mixture was heated to reflux for 5 hours. After cooling to room temperature, 400 ml of acetonitrile was added and stirred well, and then the filtrate obtained by suction filtration was concentrated to obtain 7.30 g of product. ¹ H, ¹³ C—N M R spectrum (solvent: deuterated chloroform) By measurement, it was confirmed that the obtained compound was a compound represented by the target compound (G-1).

(Synthesis of imido acid anion G-2)

Compound G-2 was obtained in the same manner as in the synthesis of G-1, except that 3,4-difluorobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-3)
Compound G-3 was obtained in the same manner as in the synthesis of G-1, except that p-fluorobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-4)
Compound G-4 was obtained in the same manner as in the synthesis of G-1, except that 3,5-bis (trifluoromethyl) benzenesulfonyl chloride was used in place of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-5)
Compound G-5 was obtained in the same manner as in the synthesis of G-1, except that p-trifluoromethylbenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-6)

Compound G-6 was obtained in the same manner as in G-1, except that p-trifluoromethoxybenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-7)

Compound G-7 was obtained in the same manner as in the synthesis of G-1, except that p-trifluoromethylbenzenesulfonamide was used instead of trifluoromethanesulfonamide.

(Synthesis of imido acid anion G-8)
The above compound G-8 was obtained in the same manner as in the synthesis of G-1, except that 2,5-difluorobenzenesulfonamide was used instead of trifluoromethanesulfonamide.

(Synthesis of imido acid anion G-9)
Compound G-9 was obtained in the same manner as in the synthesis of G-1, except that p-trifluoromethoxybenzenesulfonamide was used instead of trifluoromethanesulfonamide.

Compound G-10 was obtained in the same manner as in the synthesis of G-1, except that 2-naphthalenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-11)
Compound G-11 was obtained in the same manner as in the synthesis of G-1, except that p-toluenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-12)
Compound G-12 was obtained in the same manner as in the synthesis of G-1, except that p-nitrobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-13)
Compound G-13 was obtained in the same manner as in the synthesis of G-1, except that 4-biphenylsulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-14)
Compound G-14 was obtained in the same manner as in the synthesis of G-1, except that methanesulfonamide was used instead of trifluoromethanesulfonamide, and 2-thiophenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-15)

Compound G-15 was obtained in the same manner as in the synthesis of G-1, except that methanesulfonamide was used instead of trifluoromethanesulfonamide and benzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-16)
Compound G-16 was obtained in the same manner as in the synthesis of G-1, except that cyclopropanesulfonamide was used instead of trifluoromethanesulfonamide and benzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-17)

Compound G-17 was obtained in the same manner as in the synthesis of G-1, except that benzenesulfonamide was used instead of trifluoromethanesulfonamide and 1-octanesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-18)

The intermediate G-18a was obtained in the same manner as in the synthesis of G-1, except that p-acetamidobenzenesulfonyl chloride was used instead of pentafluorobenzenesulfonyl chloride.

To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube, 3.86 g of compound G-18a and 15 ml of 5% hydrochloric acid were added, followed by heating and stirring at 90 ° C. for 2 hours. After cooling to room temperature, the mixture was neutralized with a saturated aqueous solution of sodium bicarbonate and concentrated with an evaporator to obtain a white solid. This was washed with tetrahydrofuran during suction filtration, and the obtained filtrate was concentrated to obtain 3.03 g of a product. ¹ H, ¹³ C—N M R spectrum (solvent: deuterated chloroform) By measurement, the obtained compound was confirmed to be a compound represented by the target compound (G-18).

(Synthesis of imido acid anion G-19)

After adding 3.03 g of compound G-18, 18.4 g of cyanuric chloride, and 40 ml of water to a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube, the mixture was stirred at room temperature for 1 hour. Next, 0.93 g of aniline hydrochloride was added and stirred for 2 hours. Moreover, 0.73 g of butylamine hydrochloride was added, and the mixture was heated and stirred at 80 ° C. for 3 hours. After cooling to room temperature, salting out with sodium chloride gave 5.30 g of product. ¹ H, ¹³ C—N M R spectrum (solvent: deuterated chloroform) By measurement, the obtained compound was confirmed to be the compound represented by the target compound (G-19).

(Synthesis of imido acid anion G-20)

Compound G-20 was obtained in the same manner as in the synthesis of G-1, except that 2,3-dihydrobenzofuran-5-sulfonyl chloride was used in place of pentafluorobenzenesulfonyl chloride.

(Synthesis of imido acid anion G-21)

In a 300 ml eggplant flask containing a stir bar, tetrahydrofuran in which compound G-183.03 g was dissolved and 1,4-dioxane in which 1.07 g of maleic anhydride was dissolved were mixed at a volume ratio of 1: 1. Combined and stirred at room temperature for 12 hours. The white solid produced by the reaction was separated by suction filtration to obtain 3.81 g of the product (G-21a). ¹ H, ¹³ C—N M R spectrum (solvent: deuterated chloroform) By measurement, the obtained compound was confirmed to be a compound represented by the target compound (G-21a).

An acetic anhydride solution containing sodium acetate (sodium acetate: acetic anhydride = 1: 10) and 4.01 g of compound G-21a were added to a 300 ml eggplant flask containing a stir bar, and the mixture was stirred at 70 ° C. for 3 hours. After allowing to cool to room temperature, diethyl ether was added and the resulting precipitate was obtained by suction filtration. Thereafter, it was washed with acetonitrile, and diethyl ether was added to the filtrate for reprecipitation to obtain 3.45 g of a product. ¹ H, ¹³ C—N M R spectrum (solvent: deuterated chloroform) By measurement, the obtained compound was confirmed to be a compound represented by the target compound (G-21).

<Method for producing salt-forming compound>
(Salt-forming compound (ZC-1))
A salt-forming compound (ZC-1) comprising a cationic dye and imido acid anion (G-1) was produced by the following procedure.

  13.7 parts of imidic acid anion (G-1) and 10 parts of cationic dye (Y-1) were dissolved in a mixed solvent of 100 parts of water, 300 parts of methanol, 100 parts of methyl ethyl ketone, and 100 parts of acetone, The mixture was stirred at 60 ° C. for 240 minutes and sufficiently reacted. Then, the solid which is a salt-forming compound was taken out by removing the solvent under reduced pressure using an evaporator and concentrating. To this solid, 1000 parts of water was added and stirred at 25 ° C. for 180 minutes, followed by suction filtration to remove by-product salts. The salt-forming compound remaining on the filter paper was further washed by sprinkling 400 parts of water to completely remove the by-product salt, and then the salt-forming compound was taken out. The extracted salt-forming compound was dried with a dryer to obtain 19.0 parts of a salt-forming compound (ZC-1) of a cationic dye (Y-1) and an imido acid anion (G-1).

(Salt-forming compound (ZC-2 to ZC-99))
Various cationic dyes and various imidoic acid anions were used in the same manner as the salt-forming compound (ZC-1) except that the types and parts by weight of the cationic dye and imidoic acid anion were changed to the contents shown in Tables 5-6. A salt-forming compound consisting of (ZC-2 to ZC-99) was produced.

(Salt-forming compound (ZC-100 to ZC-102))
Various cationic properties were obtained in the same manner as the salt-forming compound (ZC-1) except that the types and parts by weight of the cationic dye and imidoic acid anion were changed to the types and parts by weight of the cationic dye and anion shown in Table 7. Salt-forming compounds (ZC-100 to ZC-102) composed of a dye and various anions were produced.

<Method for producing dye paste and coloring composition>
[Example 1]
(Preparation of dye paste DP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed 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. A colored composition (DP-1) was produced by filtration using a filter.
Salt-forming compound (ZC-1): 10.0 parts Binder resin solution 1: 50.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts

(Preparation of colored composition (DB-1))
Next, when the pigment paste (PP-7) and the dye paste (DP-1) are dried, the chromaticity of the coating film is x = 0 in a microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). .290, y = 0.600, and the mixture was stirred and mixed with a disper for 1 hour to obtain a colored composition (DB-1).

[Examples 2 to 217, Comparative Examples 1 to 9]
(Preparation of dye paste (DP-2 to 99, DP-100 to 102))
Dye pastes DP-2 to 99 and DP-100 to 102 were prepared in the same manner as dye paste DP-1, except that the types of salt-forming compounds shown in Tables 8 and 9 were changed.
(Preparation of colored composition (DB-2 to 217, 237 to 245))
Next, colored compositions (DB-2 to 217, 237 to 245) were produced in the same manner as the colored composition DB-1, except that the types of pigment paste and dye paste shown in Tables 10 to 15 were changed.
Examples 7 to 21, 38 to 52, 62 to 76, 83 to 97, 106 to 120, 137 to 151, 161 to 175, and 182 to 196 are reference examples.

[Examples 218 to 236, Comparative Examples 10 to 12]
(Preparation of dye paste (DP-2 to 99, DP-100 to 102))
Dye pastes DP-2 to 99 and DP-100 to 102 were prepared in the same manner as dye paste DP-1, except that the types of salt-forming compounds shown in Tables 8 and 9 were changed.
(Preparation of colored composition (DB-218-236, 246-248))
Next, except that the blending ratio was changed so that the types of pigment paste and dye paste shown in Tables 10 to 15 and the chromaticity of the dried coating film were x = 0.661 and y = 0.323, the coloring composition DB- In the same manner as in Example 1, colored compositions (DB-218 to 236, 246 to 248) were produced.

<Evaluation of coloring composition>
About the obtained coloring composition (DB-1 to 248), the test regarding heat resistance, lightness, and contrast ratio was done by the following method. The result of a test is shown to Tables 10-15.

(Evaluation of heat resistance of coating film)
The coloring composition (DB-1 to 248) is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was heat-treated at 220 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0
×: ΔEab * is 3.0 or more

(Lightness evaluation of coating film (when using pigment paste PP5, 6, 7))
The coloring composition (DB-1 to 217, 237 to 245) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater so that y = 0.600, and 230 ° C. in an oven. Was baked for 30 minutes to obtain a coated substrate of the obtained colored composition. The brightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. X is a difficult level to use.
◎: 59.5 or more ○: 58.0 or more, less than 59.5 ×: less than 58.0

(Lightness evaluation of coating film (when using pigment paste PP8))
The coloring composition (DB-218 to 236, 246 to 248) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater so that x = 0.661, and 230 ° C. in an oven. Was baked for 30 minutes to obtain a coated substrate of the obtained colored composition. The brightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. X is a difficult level to use.
A: 18.0 or more
○: 17.6 or more, less than 18.0 ×: less than 17.6

(Evaluation of contrast ratio of coating film (when using pigment paste PP5, 6, 7))
Films after heat treatment at 230 ° C. with coloring compositions (DB-1 to 217, 237 to 245) on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater and changing the number of rotations Three coated substrates were prepared so that the thickness was about 1.5 μm. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 230 ° C. after coating, respectively, and the film thickness and contrast ratio were measured, and the contrast at a film thickness of 1.5 μm was determined from the three-point data by the primary correlation method. It was. X is a difficult level to use.
◎: 4000 or more ○: 3500 or more, less than 4000 Δ: 3000 or more, less than 3500 ×: less than 3000

(Evaluation of contrast ratio of coating film (when using pigment paste PP8))
Films after heat treatment at 230 ° C. with coloring compositions (DB-218 to 236, 246 to 248) on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater and changing the number of rotations Three coated substrates were prepared so that the thickness was about 1.5 μm. Drying conditions were 20 minutes at 70 ° C. and 30 minutes at 230 ° C. after coating, respectively, and the film thickness and contrast ratio were measured, and the contrast at a film thickness of 1.5 μm was determined from the three-point data by the primary correlation method. It was. X is a difficult level to use.
◎: 10,000 or more ○: 5000 or more, less than 10,000 Δ: 3000 or more, less than 5000 ×: less than 3000

The coloring composition (DB-1 to 236) containing a cationic dye specific to the present application and a salt-forming compound specific to the imidic acid anion as the coloring agent has excellent results in terms of heat resistance, contrast ratio, and brightness. It became.
Moreover, the coloring composition (DB-1-13, 18-44, 49-68, 73-89, 94-112, 117- containing the salt-forming compound which contains a fluorine atom in an imido acid anion as a coloring agent especially. 143, 148 to 167, 172 to 188, 193 to 236) are coloring compositions containing a salt-forming compound containing no fluorine atom in the imidoic acid anion as a colorant (DB-14 to 17, 45 to 48, 69). -72, 90-93, 113-116, 144-147, 168-171, 189-192), the acidity of the imidoic acid anion of the counter is increased, and the solubility of the coloring composition is improved, so that the heat resistance is improved. Good results.
Among them, a coloring composition containing 4 or more fluorine atoms in an imidoic acid anion as a coloring agent (DB-1 to 9, 22 to 40, 53 to 64, 77 to 85, 98 to 108, 121 to 139, 152-163, 176-184, 197-236), since the acidity of the imido acid anion becomes stronger as a colorant, the solubility of the colored composition is further improved, not only heat resistance but also high brightness, high Contrast ratio and good results.
However, a coloring composition (DB-237 to 248) containing a salt-forming compound of a specific cationic dye of the present application and an anion which is not a specific imidoic acid anion as a colorant is greatly inferior in heat resistance as compared with Examples. Therefore, the coating film was rough, and as a result, the contrast ratio and brightness were greatly deteriorated.

<Production of photosensitive coloring composition (resist material)>
[Example 237]
(Resist material (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali developing resist material (R-1).
Coloring composition (DB-1): 60.0 parts Binder resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts

[Examples 238 to 475, Comparative Examples 13 to 24]
(Resist material (R-2 to 239, 240 to 251)
Hereinafter, the alkali developing resist material (R-2 to 251) was changed in the same manner as the resist material (R-1) except that the coloring composition (DB-1) was changed to the coloring composition shown in Tables 16 to 21. Produced.
Examples 243 to 257, 274 to 288, 298 to 312, 319 to 333, 342 to 356, 373 to 387, 397 to 411, and 418 to 432 are reference examples.

<Evaluation of photosensitive coloring composition (resist material)>
About the obtained resist material (R-1 to 251), the test regarding heat resistance, brightness, contrast ratio, and foreign material evaluation was performed by the following method. The result of a test is shown to Tables 16-21.

(Evaluation of heat resistance of coating film)
The obtained resist material (R-1 to 251) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain an ultrahigh pressure mercury lamp. Was exposed to ultraviolet light at an integrated light quantity of 150 mJ / cm ² and developed with an alkaline developer at 23 ° C. Subsequently, the coating-film board | substrate was produced by heating and standing to cool at 220 degreeC for 30 minutes. The prepared coated substrate was heat-treated at 220 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated according to the following criteria.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0
×: ΔEab * is 3.0 or more

(Lightness evaluation of coating film (when using pigment paste PP5, 6, 7))
The obtained resist material (R-1 to 217, 237 to 248) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater so that y = 0.600, and 50 mJ / cm. After being exposed to ultraviolet rays at an exposure amount of ^2, the film was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds and baked at 230 ° C. for 30 minutes in an oven. The resulting photosensitive coloring composition A coated substrate was obtained. The brightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. X is a difficult level to use.
◎: 59.5 or more ○: 58.0 or more, less than 59.5 ×: less than 58.0

(Lightness evaluation of coating film (when using pigment paste PP8))
The coloring composition (R-218 to 236, 249 to 251) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater so that x = 0.661, and 230 ° C. in an oven. Was baked for 30 minutes to obtain a coated substrate of the obtained colored composition. The brightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKA LCF-1100M). Judgment criteria are as follows. X is a difficult level to use.
A: 18.0 or more
○: 17.6 or more, less than 18.0 ×: less than 17.6

(Evaluation of contrast ratio of coating film (when using pigment paste PP5, 6, 7))
The obtained resist material (R-1 to 217, 237 to 248) was subjected to heat treatment at 230 ° C. on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater and changing the number of rotations. Is applied to three substrates so that the film thickness is about 1.5 μm, then dried at 70 ° C. for 20 minutes, and exposed to ultraviolet light with an integrated light quantity of 150 mJ / cm ² using an ultra-high pressure mercury lamp. Development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Subsequently, after heating at 220 ° C. for 30 minutes and allowing to cool, the film thickness and contrast ratio of each of the obtained coating film substrates were measured, and the contrast at a film thickness of 1.5 μm was determined from the three points of data by the primary correlation method. X is a difficult level to use.
◎: 4000 or more ○: 3500 or more, less than 4000 Δ: 3000 or more, less than 3500 ×: less than 3000

(Evaluation of contrast ratio of coating film (when using pigment paste PP8))
The obtained resist material (R-218 to 236, 249 to 251) was subjected to heat treatment at 230 ° C. on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater while changing the rotation speed. Is applied to three substrates so that the film thickness is about 1.5 μm, then dried at 70 ° C. for 20 minutes, and exposed to ultraviolet light with an integrated light quantity of 150 mJ / cm ² using an ultra-high pressure mercury lamp. Development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Subsequently, after heating at 220 ° C. for 30 minutes and allowing to cool, the film thickness and contrast ratio of each of the obtained coating film substrates were measured, and the contrast at a film thickness of 1.5 μm was determined from the three points of data by the primary correlation method. X is a difficult level to use.
◎: 10,000 or more ○: 5000 or more, less than 10,000 Δ: 3000 or more, less than 5000 ×: less than 3000

The photosensitive coloring composition (R-1 to 239) containing a cationic dye specific to the present application and a salt-forming compound specific to the imidic acid anion as a colorant is very good in terms of heat resistance, contrast ratio, and brightness. It became a result.
Moreover, the photosensitive coloring composition (R-1-13, 18-44, 49-68, 73-89, 94-112, 117 containing the salt-forming compound which contains a fluorine atom in an imido acid anion as a coloring agent especially. ˜143, 148 to 167, 172 to 188, 193 to 239) are photosensitive coloring compositions ((R-14 to 17, 45) containing a salt-forming compound containing no fluorine atom in the imido acid anion as a colorant. -48, 69-72, 90-93, 113-116, 144-147, 168-171, 189-192), the acidity of the imidic acid anion of the counter is increased and the solubility of the coloring composition is improved. The results showed good heat resistance.
Among them, further, a photosensitive coloring composition (R-1 to 9, 22 to 40, 53 to 64, 77 to 85, 98 to 108, 121 to 1) containing 4 or more fluorine atoms in the imidoic acid anion as a coloring agent. 139, 152-163, 176-184, 197-239), the acidity of the imido acid anion becomes stronger as the colorant, so that the solubility of the colored composition is further improved, and not only heat resistance but also high brightness. High contrast ratio and good results.
However, the photosensitive coloring composition (R-240 to 251) containing a salt-forming compound of a specific cationic dye of the present application and an anion which is not a specific imidoic acid anion as a colorant has higher heat resistance than the examples. The coating film was rough because it was greatly inferior, and as a result, the contrast ratio and brightness were greatly inferior.

<Manufacture of color filters>
First, the blue photosensitive coloring composition used for preparation of a color filter was produced.

(Preparation of blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).
Pigment paste (PP-1) 24.0 parts Pigment paste (PP-2) 10.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator ("Irgacure 907" manufactured by BASF) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

(Production of color filter)
A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (R-218) was applied on the substrate with a spin coater so as to have a film thickness of 2.0 μm to form a colored film. The film was irradiated with ultraviolet rays of 300 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. By the same method, the green photosensitive coloring composition (R-100) of the present invention has a thickness of 2 um, and the blue photosensitive coloring composition (RB-1) has a thickness of 2 um. Each was coated to form a green filter segment and a blue filter segment to obtain a color filter.

By using the red photosensitive coloring composition (R-218) and the green photosensitive coloring composition (R-100) of the present invention, it was possible to produce a color filter having a high contrast ratio and high brightness. .

Claims (6)

A color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is a salt-forming compound of an imidoanion and a cationic dye represented by the following general formula (1): A colored composition for a color filter.
General formula (1)
[In General Formula (1), D ⁺ represents a cationic dye having a maximum absorption wavelength of 360 nm to 500 nm, R ¹ represents an aliphatic hydrocarbon group which may have a substituent, and R ² represents a fluorine atom. Is an aromatic hydrocarbon group . ] The cationic dye pigment is at least one cationic dye pigment selected from the group consisting of methine pigments, azo pigments, auramine pigments, acridine pigments, cetoflavine pigments, coumarin pigments, and azomethine pigments . The coloring composition for a color filter according to claim 1, which is contained. The coloring composition for a color filter according to claim 1 or 2 , wherein in the general formula (1), R ¹ is a trifluoromethyl group, and R ² is a pentafluorophenyl group. Furthermore, the coloring composition for color filters in any one of 1-3 containing an organic dye and / or an organic pigment. Furthermore, the coloring composition for color filters in any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator. A color filter comprising a filter segment formed from the colored composition for a color filter according to any one of claims 1 to 5 on a substrate.