JP2014108975A - Color material, color material dispersion liquid, colored resin composition for color filter, color filter, liquid crystal display and organic light-emitting display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color material excellent in heat resistance.SOLUTION: The color material is represented by the specified general formula (I). (The symbols in the general formula (I) are as described in the specifications.)

Description

  The present invention relates to a color material, a color material dispersion, a colored resin composition for a color filter, a color filter, a liquid crystal display device, and an organic light emitting display device.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of home-use liquid crystal televisions is also increasing, and the market for liquid crystal displays is expanding. Recently, an organic light-emitting display device such as an organic EL display having high visibility due to self-emission has been attracting attention as a next-generation image display device. In the performance of these image display devices, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, in the formation of a color image of a liquid crystal display device, the light passing through the color filter is colored as it is into the color of each pixel constituting the color filter, and the light of those colors is synthesized to form a color image. In the organic light emitting display device, when a color filter is used for the white light emitting organic light emitting element, a color image is formed as in the liquid crystal display device.
Under such circumstances, there are increasing demands for higher brightness, higher contrast, and improved color reproducibility in color filters.

When the colored layer of the color filter is formed, a colored layer forming resin composition having a pigment or a dye is used as the coloring material. The pigment is generally excellent in various resistances such as heat resistance as compared with the dye, but the brightness of the produced color filter may be insufficient.
On the other hand, when a dye is used as a color material, a color filter with high luminance can be produced, but there is a problem that various resistances and contrast are insufficient.

As a technique for improving various resistances of dyes, a technique for forming a salt-forming compound is known (for example, Patent Documents 1 to 3).
Patent Document 1 describes an example in which a chloride ion or an aryl sulfate ion is used as a counter anion of a triarylmethane dye. Patent Document 2 describes a technique in which a sulfonated product of a dye skeleton such as phthalocyanine or anthraquinone is used as a counter anion to form a salt with a triarylmethane skeleton that is a cation. Patent Document 3 describes a salt-forming compound comprising a triarylmethane basic dye and an organic sulfonated product having at least two sulfone groups.

On the other hand, Patent Documents 4 and 5 discuss a technique of combining a plurality of dye skeletons.
Patent Document 4 discloses a double triphenylmethane dye in which two triphenylmethane cations are bonded. According to Patent Document 4, the double triphenylmethane dye is excellent in dyeing properties. However, the heat resistance was insufficient.

  Patent Document 5 describes a polysiloxane dye highly crosslinked by a polysiloxane containing at least 10 Si atoms. The polysiloxane dye described in Patent Document 5 is a mixture containing an unreacted compound having only one dye skeleton and dyes having different degrees of polymerization due to its synthesis method. In the polysiloxane dye, there is a problem that it is difficult to separate only a dye having a specific polymerization degree, and productivity is poor. Since the polysiloxane dye has a silanol group or an alkoxysilyl group, a siloxane bond is formed between the dyes or another component having a silanol group or an alkoxysilyl group, so that the solubility changes, dispersion stability, etc. Since the state of the solution or the dispersion changes with time, for example, the solution or the dispersion is difficult to handle. Since such a reaction is likely to proceed particularly during heating, it was not a dye suitable for color filter applications.

  Under such circumstances, the present inventors have provided a color material containing a specific cation in which a plurality of color material skeletons are crosslinked by a crosslinking group, a divalent or higher anion, and a color filter using the color material. (Patent Documents 6 and 7). The color materials described in Patent Documents 6 and 7 are excellent in heat resistance, and a color filter using the color material has high contrast, excellent solvent resistance and electrical reliability.

JP 2008-304766 A International Publication No. 2009/107734 Pamphlet JP 2011-7847 A JP 54-5030 A Special table 2010-526897 gazette International Publication No. 2012/144520 Pamphlet International Publication No. 2012/144521 Pamphlet

  The present inventor has examined further improvement of heat resistance of the color material in order to improve the process margin of the high-temperature heating process at the time of manufacturing the color filter.

  The present invention has been made in view of the above circumstances, a color material excellent in heat resistance, a color material dispersion capable of forming a coating film excellent in heat resistance using the color material, and excellent in heat resistance. To provide a colored resin composition for a color filter capable of forming a colored layer, a color filter formed using the colored resin composition for a color filter, a liquid crystal display device having the color filter, and an organic light emitting display device And

  The coloring material according to the present invention is a compound represented by the following general formula (I).

(In general formula (I), A represents an a-valent aromatic group, B ^c- represents a c-valent anion. R ^{1 to} R ⁵ each independently have a hydrogen atom or a substituent. R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring structure, and Ar ¹ has a substituent. And a plurality of R ^{1 to} R ⁵ and Ar ¹ may be the same or different from each other.
a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

The color material dispersion according to the present invention comprises a color material represented by the following general formula (I), a dispersant, and a solvent having a solubility of the color material at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It is characterized by containing.
(In general formula (I), A represents an a-valent aromatic group, B ^c- represents a c-valent anion. R ^{1 to} R ⁵ each independently have a hydrogen atom or a substituent. R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring structure, and Ar ¹ has a substituent. And a plurality of R ^{1 to} R ⁵ and Ar ¹ may be the same or different from each other.
a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

  In the colorant dispersion according to the present invention, it is preferable that the solvent is an ester solvent from the viewpoint of substantially not dissolving the colorant and solubility of other components and application suitability.

  In the colorant dispersion according to the present invention, the dispersant is preferably a polymer dispersant containing a nitrogen atom in the main chain or side chain from the viewpoint of improving the dispersibility and dispersion stability of the colorant.

  The colored resin composition for a color filter according to the present invention includes at least the color material dispersion according to the present invention, a binder component, and a solvent. By including the colorant dispersion according to the present invention, the colored resin composition for a color filter according to the present invention is preferable because it has excellent heat resistance and can achieve high contrast of the colored layer.

The present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is formed by curing the colored resin composition for a color filter. The color filter is characterized by being a colored layer.
According to another aspect of the present invention, there is provided a liquid crystal display device comprising the color filter, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Furthermore, the present invention provides an organic light emitting display device comprising the color filter and an organic light emitter.

  According to the present invention, a color material excellent in heat resistance, a color material dispersion capable of forming a coating film excellent in heat resistance using the color material, and a color filter capable of forming a colored layer excellent in heat resistance A colored resin composition, a color filter formed using the colored resin composition for a color filter, a liquid crystal display device having the color filter, and an organic light emitting display device can be provided.

It is the schematic which shows an example of the color filter of this invention. It is the schematic which shows an example of the liquid crystal display device of this invention. It is the schematic which shows an example of the organic light emitting display apparatus of this invention.

Hereinafter, the color material, the color material dispersion, the color resin composition for color filter, the color filter, the liquid crystal display device and the organic light emitting display device according to the present invention will be described in order.
In the present invention, light includes electromagnetic waves having wavelengths in the visible and invisible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.

[Color material]
The coloring material according to the present invention is a compound represented by the following general formula (I).

(In general formula (I), A represents an a-valent aromatic group, B ^c- represents a c-valent anion. R ^{1 to} R ⁵ each independently have a hydrogen atom or a substituent. R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring structure, and Ar ¹ has a substituent. And a plurality of R ^{1 to} R ⁵ and Ar ¹ may be the same or different from each other.
a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )

The color material according to the present invention is excellent in heat resistance. The reason is unclear, but is estimated as follows.
Dyes generally have a problem of low heat resistance. As a means for overcoming this problem, a technique of making a dye skeleton multimer has been studied (for example, Patent Documents 4 to 7). In any of the methods of Patent Documents 4 to 7, the dye skeleton is cross-linked through sp ³ carbon.
Colorant of the present invention contrast, N included in the cation moiety (nitrogen atom) is, because with direct coupling structure with an atom constituting the aromatic ring of the aromatic group, than through the sp ³ carbon Also, the overall fastness of the cation is improved. Therefore, a salt-formation product composed of a divalent or higher cation having a structure represented by the following general formula (II) is more stable than a conventional dye multimer, becomes less hydrated, and has heat resistance. It is estimated to improve. Furthermore, the structure represented by the following general formula (II) has a higher hydrophobicity because the linking group A is an aromatic group, and, when combined with the stability of the bond, becomes substantially insoluble in water. Presumed.
Moreover, since the coloring material of the present invention has high hydrophobicity as described above, it is presumed to suppress dissociation of ion pairs and decomposition of cation moieties. As a result, the heat resistance of the color material represented by the general formula (I) is improved, and the color material is not easily faded even in a high-temperature heating process at the time of manufacturing a color filter, and a colored layer having excellent contrast can be obtained. .

(In the general formula (II), A, R ^{1 to} R ⁵ , Ar ¹ , a and e are the same as those in the general formula (I).)

  E in the general formula (I) is an integer of 0 or 1. When e is 0, it has a triarylmethane skeleton represented by the following general formula (III).

(In the general formula (III), R ^{1 to} R ⁵ and Ar ¹ are the same as in the general formula (I).)

  Moreover, when e is 1, it has a xanthene skeleton represented by the following general formula (IV).

(In General Formula (IV), R ^{1 to} R ⁵ and Ar ¹ are the same as in General Formula (I).)

  A plurality of e may be the same or different. That is, for example, it may be a cation moiety having only a triarylmethane skeleton or a plurality of xanthene skeletons, or may be a cation moiety containing both a triarylmethane skeleton and a xanthene skeleton in one molecule. The color material of the general formula (I) can be adjusted to a desired color by combining the skeleton of the cation part and the combination of substituents described later.

A in the general formula (I) is an a-valent aromatic group. Since A has a structure in which an atom constituting an aromatic ring and a nitrogen atom contained in the cation portion are directly bonded to each other, the fastness of the entire cation is improved and heat resistance is excellent.
The aromatic group in A may be a heterocyclic group in addition to an aromatic hydrocarbon group composed of a carbocyclic ring. As aromatic hydrocarbon in the aromatic hydrocarbon group, in addition to benzene ring, condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring; biphenyl, terphenyl, etc. And a chain polycyclic aromatic hydrocarbon. On the other hand, the heterocyclic ring in the heterocyclic group includes 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole and pyrazole; 6-membered heterocycles such as pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine and pyrazine. And condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline and the like. These aromatic groups may have a substituent.
Examples of the substituent that the aromatic group may have include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, an alkyl group having 1 to 5 carbon atoms, a carboxy group, and an amino group.

  A is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic group composed of a condensed polycyclic carbocycle having 6 to 14 carbon atoms. Among them, a group containing a benzene ring or a naphthalene ring is preferable from the viewpoint of simple structure and inexpensive raw material, and a group containing a benzene ring is more preferable.

  The valence a in A is the number of chromogenic cation sites constituting the cation, and a is an integer of 2 or more. In the coloring material of the present invention, since the cation valence a is 2 or more, the colorant is excellent in heat resistance, and among them, the cation valence a is preferably 3 or more. The upper limit of a is not particularly limited, but a is preferably 4 or less, and more preferably 3 or less, from the viewpoint of ease of production.

The alkyl group in R ^{1 to} R ⁵ is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms can be mentioned, among which a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a straight chain having 1 to 5 carbon atoms. A chain or branched alkyl group is more preferred from the viewpoint of ease of production and raw material procurement. Especially, it is especially preferable that the alkyl group in R < ¹ > -R < ⁵ > is an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group, and examples of the substituted alkyl group include a benzyl group.
The aryl group in R ^{1 to} R ⁵ is not particularly limited. For example, a phenyl group, a naphthyl group, etc. are mentioned. Examples of the substituent that the aryl group may have include an alkyl group and a halogen atom.

R ² and R ³ , R ⁴ and R ⁵ are combined to form a ring structure. R ² and R ³ , R ⁴ and R ⁵ form a ring structure through a nitrogen atom. Say. The ring structure is not particularly limited, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Among them, from the viewpoint of chemical stability, R ^{1 to} R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or R ² and R ³ , or R ⁴ and R ^5. Thus, it is preferable to form a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R ^{1 to} R ⁵ can each independently have the above structure. Among them, R ¹ is preferably a hydrogen atom from the viewpoint of color purity, and R ² to R ² are preferably from the viewpoint of ease of production and raw material procurement. More preferably, all R ⁵ are the same.

The divalent aromatic group in Ar ¹ is not particularly limited. As the aromatic group for Ar ^1, the same aromatic groups as those described for the aromatic group for A can be used.
Ar ¹ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthylene group is more preferable because the structure is simple and the raw material is inexpensive.

A plurality of R ^{1 to} R ⁵ and Ar ¹ in one molecule may be the same or different. A desired color can be adjusted by a combination of R ^{1 to} R ⁵ and Ar ¹ .

In the color material according to the present invention, the anion portion (B ^c− ) is not particularly limited, and may be an organic anion or an inorganic anion. Here, the organic anion represents an anion containing at least one carbon atom. Moreover, an inorganic anion represents the anion which does not contain a carbon atom.

When B < ^- > is an organic anion, the structure is not particularly limited. Among these, an organic group having an anionic substituent is preferable. The organic group refers to a group containing a carbon atom.
Examples of the anionic substituent include —SO ₂ N ^— SO ₂ CH ₃ , —SO ₂ N ^— COCH ₃ , —SO ₂ N ^— SO ₂ CF ₃ , —SO ₂ N ^— COCF ₃ , —CF ₂ SO _{2. ^{N - SO 2 CH 3, -CF}} 2 SO 2 N - COCH 3, -CF 2 SO 2 N - SO 2 CF 3, -CF 2 SO 2 N - COCF 3 or imidate group such as, -SO ₃ ^-, Substituents such as —CF ₂ SO ₃ ^— , —PO ₃ ²⁻ , —COO ⁻ , —CF ₂ PO ₃ ²⁻ , —CF ₂ COO ^{— and the} like can be mentioned.
Among them, ease and manufacturing cost of raw materials available, from the viewpoint high effect of maintaining the color-developed state is stabilized cations by high acidity, and imidate _{^{groups, -SO 3 -, -CF 2 SO}} 3 - are preferred, further It is preferably —SO ₃ ^— (sulfonato group).
When B ^c- is a divalent or higher organic anion, using an organic anion containing two or more monovalent anionic substituents in one molecule stabilizes the cation and stabilizes the coloring of the coloring material. It is preferable from the point of making it.
When a plurality of anionic substituents are substituted, the same substituent may be used, or different substituents may be used.

Examples of the organic group in which the anionic substituent is substituted include a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, a monocyclic or polycyclic aromatic group, and a group in which these are combined. The carbon chain may contain hetero atoms such as O, S, and N, may contain a carbonyl group, a carboxy group, an oxycarbonyl group, an amide group, or may have a hydrogen atom substituted. Good. Examples of the substituent that the organic group may have include a halogen atom.
Examples of the organic group in which the anionic substituent is substituted include cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, bicyclo [2,2,2] hexane, bicyclo [3,2,3] octane, adamantane, and the like. Hydrocarbons such as benzene, naphthalene, anthracene, phenanthrene, pyrene, triphenylene, fluorene, furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, triazine, indole, purine, quinoline, isoquinoline, xanthene, carbazole, etc. Group compounds, and further may have a substituent such as a halogen atom or an alkyl group.
Among them, the organic group to be substituted with the anionic substituent is preferably a monocyclic or polycyclic aromatic hydrocarbon group or a group in which these are combined from the viewpoint of easy introduction of the anionic substituent.

  For the purpose of preventing color change by anions, it is preferable to use an organic group having an absorption maximum in a wavelength region of 400 nm or less. Examples of the organic group having an absorption maximum in a wavelength region of 400 nm or less include organic groups composed of condensed polycyclic aromatic hydrocarbons such as naphthalene, tetralin, indene, fluorene, anthracene, and phenanthrene; biphenyl, terphenyl, diphenylmethane, and triphenyl Organic groups composed of chain polycyclic hydrocarbons such as phenylmethane and stilbene; Organic groups composed of 5-membered heterocycles such as furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyridazine, Organic groups consisting of 6-membered heterocycles such as pyrimidine and pyrazine; from condensed polycyclic heterocycles such as benzofuran, thionaphthene, indole, carbazole, coumarin, benzo-pyrone, quinoline, isoquinoline, acridine, phthalazine, quinazoline, quinoxaline Organic group, and the like that.

Moreover, as an organic group substituted with an anionic substituent, a skeleton derived from an azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye and phthalocyanine dye, indigo dye, which is an organic compound or an organometallic compound, is used. Also good. Alternatively, conventionally known acid dyes, direct dyes, and acid mordant dyes may be used. Specific examples of the acid dye, the direct dye, and the acid mordant dye include those described in International Publication No. 2012/144520 pamphlet. An anionic substituent may be further introduced into the dye to change the valence of the anion.
When a dye-derived skeleton, acid dye, direct dye, acid mordant dye, or the like is used, the color tone of the obtained color material changes, and the color tone of the color material represented by the general formula (I) is desired. Can be adjusted.

  In the coloring material according to the present invention, the organic anion is preferably an anion represented by the following general formula (V) from the viewpoint of improving heat resistance.

(In General Formula (V), Ar ² is a c-valent aromatic group which may have a substituent. C represents an integer of 1 or more.)

  When the anion of the above general formula (V) is used as the anion part of the color material of the present invention, the anion is colorless or pale yellow, so that the color material has a cation represented by the general formula (I). It has a feature that it is easy to maintain a unique color.

The aromatic group in Ar ² is not particularly limited. The aromatic group in Ar ² can be the same as those mentioned for the aromatic group in A.

Ar ² is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group composed of a condensed polycyclic carbocycle having 10 to 14 carbon atoms. Among these, a phenylene group or a naphthalene group is more preferable because the structure is simple and the raw material is inexpensive.

On the other hand, when B ^c− is an inorganic anion, examples of the inorganic anion include halide ions such as fluoride ion, chloride ion, bromide ion, iodide ion, nitrate ion (NO ⁻ ), peroxygen, and the like. In addition to chlorate ions (ClO ₄ ⁻ ), inorganic oxo acids and dehydrated condensates thereof may be used. Examples of the inorganic oxo acid include divalent or higher oxo acid anions (phosphate ion, sulfate ion, chromate ion, tungstate ion (WO ₄ ²⁻ ), molybdate ion (MoO ₄ ²⁻ ), etc.). And inorganic anions such as polyacid ions condensed with a plurality of oxo acids and mixtures thereof.
The polyacid may be an isopolyacid ion (M _m O _n ) ^c- or a heteropoly acid ion (X _l M _m O _n ) ^c- . In the above ionic formula, M represents a poly atom, X represents a hetero atom, m represents a composition ratio of poly atoms, and n represents a composition ratio of oxygen atoms. Examples of the poly atom M include Mo, W, V, Ti, and Nb. Examples of the hetero atom X include Si, P, As, S, Fe, and Co.
Especially, it is preferable that it is an anion of the inorganic acid containing molybdenum (Mo) and / or tungsten (W) from a heat resistant point.

As an anion of inorganic acid containing molybdenum and / or tungsten, for example, tungstate ion [W ₁₀ O ₃₂ ] ⁴⁻ , molybdate ion [Mo ₆ O ₁₉ ] ²⁻ or heteropoly acid, which is an isopolyacid, is used. , ion phosphotungstic acid _{[PW 12 O} ^{40] 3-,} silicotungstic acid ion _{[SiW 12 O} ^{40] 4-,} phosphomolybdic acid ion _{[PMo 12 O} ^{40] 3-,} phosphorus tongue strike molybdate _{[PW 12-x ^{Mo x O 40] 3-, H}} 3 [PW 2-x Mo x O 7] 4- , and the like. The anion of the inorganic acid containing molybdenum and / or tungsten is preferably a heteropolyacid among the above from the viewpoint of heat resistance and the availability of raw materials, and further a heteropolyacid containing P (phosphorus). More preferably.

  The molar ratio of molybdenum and tungsten in the polyacid anion containing molybdenum and / or tungsten is not particularly limited, but from the viewpoint of heat resistance, the molar ratio of molybdenum to tungsten is 0: 100 to 15:85. Is preferred.

In the coloring material of the present invention, the plurality of anions (B ^c− ) may be the same or different, may be used in combination with an organic anion and an inorganic anion, and are used in combination with anions having different valences. May be. Especially, it is preferable from a heat resistant point that an anion ( ^Bc- ) contains the anion more than bivalence.

In the general formula (I), b represents the number of cation moieties in the molecule, d represents the number of anion moieties in the molecule, and b and d represent an integer of 1 or more. The color material of the present invention is not limited to the case where each of b and d is 1 in the crystal or aggregate, and can take any natural number of 2, 3, 4,. From the viewpoint of heat resistance, it is preferable that at least a part of the coloring material of the present invention forms a molecular aggregate of b ≧ 2. Moreover, it is preferable that at least a part of the coloring material of the present invention forms a molecular aggregate having d ≧ 2 from the viewpoint of heat resistance.
When b is 2 or more, a plurality of cations in the molecular aggregate may be one kind alone, or two or more kinds may be combined. When d is 2 or more, the anion present in the molecular aggregate may be a single anion or a combination of two or more, and an organic anion and an inorganic anion may be used in combination. .

The coloring material according to the present invention can be used after being dissolved in a solvent. Examples of the solvent for dissolving the coloring material according to the present invention include methanol, N-methylpyrrolidone (NMP), γ-butyrolactone, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF) and the like.
On the other hand, the coloring material according to the present invention is dispersed in a solvent having a solubility of the coloring material at 23 ° C. of 0.1 (mg / 10 g solvent) or less, that is, a solvent that does not substantially dissolve or a poorly soluble solvent. Can be used. In this case, since it is dispersed in the solvent while maintaining its agglomerated state, the heat resistance is higher than when it is used after being dissolved in the solvent. In addition, since the method of dispersing and using the color material according to the present invention will be described in detail in the section of the color material dispersion described later, description thereof is omitted here.

[Production method of coloring material]
Although the manufacturing method of the color material represented by the general formula (I) is not particularly limited, it can be obtained, for example, by manufacturing a cation moiety by the following method and then introducing a desired counter anion as necessary. it can.
The cation part of the coloring material represented by the following general formula (I) according to the present invention is a condensation reaction between a compound represented by the following general formula (A) and a compound represented by the following general formula (B). Can be obtained.

(In the general formula (A) and the general formula (B), Ar ^{1 ′} represents a monovalent aromatic group in which hydrogen is bonded to Ar ¹ , and A, R ^{1 to} R ⁵ , a, and e are The same as in general formula (I).)

A dehydration condensation is performed between Ar ^{1 ′} of the general formula (A) and the carbonyl group of the general formula (B), thereby forming a xanthene skeleton substituted with a triarylmethane skeleton or an aromatic group, and at the same time, a linking group. A is introduced. According to the production method, color materials having different degrees of polymerization do not occur, and unreacted substances are easily separated because their skeletons are greatly different, and the color material according to the present invention has high purity and high yield. Can be obtained at

(Compound represented by the following general formula (A))
First, a compound represented by the following general formula (A), which is a precursor compound of the cation moiety, is synthesized. Moreover, a commercial item may be used for the compound represented by general formula (A).

(In the formula (A), A, R ¹ and a are the same as those in the general formula (I). Ar ^{1 ′} is a structure in which hydrogen is bonded to Ar ¹ in the general formula (I).)

The method for synthesizing the compound represented by the general formula (A) is not particularly limited. For example, the halogenated aromatic compound into which the desired substituent Ar ^{1 ′} is introduced and the a valence into which the desired substituent A is introduced. The amine compound can be obtained by reacting in a solvent using palladium acetate or the like as a catalyst in the presence of a base.

The amount of the halogenated aromatic compound used in the above reaction varies depending on the desired valence (a). For example, when a = 2, it is 1.5 to 10 molar equivalents relative to the amine compound. It is preferable that it is 1.5 to 3.0 molar equivalent, and further 1.8 to 2.2 molar equivalent suppresses the formation of by-products and improves the reaction yield. It is preferable from the point of making.
When a = 3, the amount of the halogenated aromatic compound used is preferably 2.5 to 10 molar equivalents and 2.5 to 4.5 molar equivalents with respect to the amine compound. Is more preferable, and is preferably 2.8 to 3.4 molar equivalents from the viewpoint of suppressing the production of by-products and improving the reaction yield.

  Although the reaction temperature in the said reaction does not have a restriction | limiting in particular, Usually, it is about 100-150 degreeC, and it is preferable that it is 130-145 degreeC from the point which suppresses a side reaction. Moreover, there is no restriction | limiting in particular in the reaction pressure of the said reaction, but normal pressure-0.1 MPa are desirable, and normal pressure is further more desirable. In addition, the reaction time in the above reaction may vary depending on the amount of synthesis, reaction temperature, etc., and thus cannot be generally specified, but is usually set in the range of 3 to 72 hours, preferably 4 to 48 hours.

  Although it does not specifically limit as a base used for the said reaction, For example, metal alkoxide, metal amide, etc. other than sodium hydroxide, potassium hydroxide, potassium carbonate etc. are mentioned. Among them, it is preferable to use a strong base with low nucleophilicity from the viewpoint of suppressing side reactions and improving the yield of the base generator. For example, potassium-t-butoxide, sodium-t-butoxide, lithium-t- Butoxide, lithium diisopropylamide, potassium hexamethyldisilazide, lithium tetramethylpiperidide and the like are preferably used. Among strong bases having low nucleophilicity, it is more preferable to use potassium t-butoxide.

  The addition amount of the base is not particularly limited, but is usually 2.0 to 4.0 molar equivalents relative to the amine compound, and 2.5 to 3.5 molar equivalents improves the reaction yield. It is preferable from the point.

In the compound represented by the general formula (A), an a-valent halogenated aromatic compound into which a desired substituent A is introduced and an amine compound into which a desired substituent Ar ^{1 ′} is introduced are the same as described above. It can also be obtained by reacting by a method.

(Synthesis of cation moiety)
The cation part of the coloring material represented by the general formula (I) is obtained by subjecting the compound represented by the general formula (A) and the compound represented by the following general formula (B) to a condensation reaction. Is synthesized. For example, it can be obtained as a chloride of the cation moiety by reacting in a solvent using a chlorinating agent such as phosphoryl chloride. A commercial item can be used for the compound represented by the following general formula (B).

(R ^{2 to} R ⁵ and e in the formula (B) are the same as those in the general formula (I).)

The amount of the compound represented by the general formula (B) used in the above reaction varies depending on the desired valence (a). For example, when a = 2, 1.5 to 4.0 molar equivalents, more preferably 1.5 to 3.0 molar equivalents, and even more preferably 1.8 to 2.2 molar equivalents by-product. From the point which suppresses the production | generation of and improves a reaction yield.
When a = 3, the amount of the compound represented by the general formula (B) is preferably 2.5 to 5.0 molar equivalents relative to the general formula (A). It is more preferable that it is 0.8-4.5 molar equivalent, and it is further preferable that it is 3.0-4.2 molar equivalent from the point which suppresses the production | generation of a by-product and improves reaction yield.

  The reaction temperature in the above reaction is not particularly limited, but is usually about 110 to 150 ° C, and preferably 110 to 120 ° C from the viewpoint of suppressing side reactions. Moreover, there is no restriction | limiting in particular in the reaction pressure of the said reaction, but normal pressure-0.1 MPa are desirable, and normal pressure is further more desirable. The reaction time in the above reaction may vary depending on the amount of synthesis, reaction temperature, etc., and thus cannot be generally stated, but is usually set in the range of 1 to 10 hours, preferably 1 to 5 hours.

  The amount of phosphorus oxychloride added is not particularly limited, but is usually 1.5 to 3.0 molar equivalents and 1.8 to 3.0 molar equivalents relative to the compound (A). This is preferable from the viewpoint of improving the yield.

  The color material represented by the general formula (I) can be obtained by mixing the cation moiety chloride obtained by the above reaction and the desired anion moiety in a solvent.

[Color material dispersion]
The color material dispersion according to the present invention comprises a color material represented by the following general formula (I), a dispersant, and a solvent having a solubility of the color material at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It is characterized by containing.

(In general formula (I), each symbol is as described above.)

  The color material dispersion according to the present invention is used by combining the color material represented by the general formula (I) and a dispersant and dispersing the color material in a solvent in which the color material is not substantially dissolved or a hardly soluble solvent. Thus, while achieving the same high brightness as that of the dye, a colorant dispersion that can achieve the demand for high contrast and can form a coating film excellent in heat resistance can be obtained.

The color material dispersion according to the present invention contains at least a color material, a dispersant, and a solvent, and may contain other components as necessary.
Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail in order, but the color material is as described above, and thus description thereof is omitted here.

(Dispersant)
In the color material dispersion according to the present invention, the color material represented by the general formula (I) is used by being dispersed in a solvent. In the present invention, a dispersant is used in order to favorably disperse the color material. The dispersant can be appropriately selected from those conventionally used as a dispersant. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.

  Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salt or (partial) alkylamine salt; (co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester or knitted product thereof; polyurethanes; unsaturated polyamides; polysiloxane Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.

  Among the polymer dispersants, among them, the colorant represented by the above general formula (I) can be suitably dispersed, and the polymer dispersion containing a nitrogen atom in the main chain or side chain from the viewpoint of good dispersion stability Agents are preferred. When a polymer dispersant containing a nitrogen atom in the main chain or side chain is used, not only the colorant represented by the general formula (I) is well dispersed but also represented by the general formula (I). It is presumed that the coloring material also has an effect of stably existing in the state of ion pairs or in the state of the molecular aggregate. As a result, a colorant dispersion having excellent heat resistance can be obtained.

Examples of the polymer dispersant containing a nitrogen atom in the main chain or side chain include (partial) amine salts, (partial) ammonium salts and (partial) of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid. Examples include alkylamine salts; polyurethanes; unsaturated polyamides; polyethyleneimine derivatives; polyallylamine derivatives.
Specific examples of the polymer dispersant containing a nitrogen atom in the main chain or side chain include those described in International Publication No. 2012/144521 pamphlet.

Among them, the polymer dispersant containing a nitrogen atom in the main chain or side chain preferably contains a polyallylamine derivative from the viewpoint of excellent heat resistance and improving contrast. Furthermore, among the polyallylamine derivatives, a graft copolymer having an allylamine derivative in the main chain, the sum of the tertiary amino group and the quaternary ammonium salt is based on the total amino groups in the graft copolymer, It is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably no tertiary amino group and quaternary ammonium salt.
When the allylamine polymer is a graft copolymer as described above, in the nitrogen portion of the main chain skeleton, the adsorptivity to the color material represented by the general formula (I) increases, and the color material is in an ion pair state. Alternatively, it can exist more stably in the state of the molecular aggregate. As a result, it is estimated that the solvent resistance and electrical reliability are further improved. On the other hand, the grafted polymer chain is soluble in the solvent, so that the colorant can be stabilized in the solvent, and as a result, the dispersibility and dispersion stability of the colorant are improved. It is estimated that the contrast is improved.

  As the dispersant, among the dispersants having a polyallylamine derivative, the polyallylamine derivative is an allylamine polymer having an amino group in the side chain, and a polyester, polyamide and / or polyesteramide having a free carboxylic acid. A graft copolymer obtained by a reaction is preferable from the viewpoints of improving the dispersibility and dispersion stability of the coloring material and being excellent in solvent resistance and electrical reliability.

  Among them, it is more preferable to have a repeating unit represented by the following general formula (i) from the viewpoint of achieving high contrast and excellent solvent resistance and electrical reliability.

(In the formula, R ¹¹ is a free amino group, a group represented by the following general formula (ii) or (iii), n represents the number of repeating units, provided that at least one of n R ¹¹ is a general group. Represents a group represented by formula (iii).)

(In the formula, R ¹² represents a residue obtained by removing a carboxyl group from either a polyester having a free carboxylic acid, a polyamide having a free carboxylic acid, or a polyester amide having a free carboxylic acid.)

  Specific examples of such polyallylamine derivatives include those described in International Publication No. 2012/144521 pamphlet.

  In the color material dispersion of the present invention, the content of the dispersant is not particularly limited as long as the effects of the present invention are not impaired. From the viewpoint of the dispersibility of the color material and the dispersion stability over time, 100 parts by mass of the color material It is preferable that it is 5-100 mass parts with respect to it, More preferably, it is 10-80 mass parts.

(solvent)
The solvent used in the present invention is a solvent that does not substantially dissolve the color material represented by the general formula (I) or a hardly soluble solvent, and the solubility of the color material at 23 ° C. is 0.1 (mg). / 10 g solvent) The following solvents. By using such a solvent, the color material dispersion according to the present invention can be used by dispersing the color material as particles (aggregates) in a solvent. The color material represented by the general formula (I) used in the present invention is excellent in solvent resistance and electrical reliability by being dispersed in a solvent while maintaining its aggregation state. Among them, a solvent having a solubility of the coloring material at 23 ° C. of 0.01 (mg / 10 g solvent) or less is preferable, and a solvent that does not substantially dissolve the coloring material is more preferable.

In the present invention, a solvent having a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less can be simply determined by the following evaluation method. Can be determined.
Into a 20 mL sample tube, 10 g of the solvent to be evaluated is added, 0.1 g of the coloring material is further added, the lid is covered, shaken well for 20 seconds, and then allowed to stand in a 23 ° C. water bath for 10 minutes. 5 g of this supernatant liquid is filtered to remove insoluble matters. The absorbance spectrum of a solution obtained by further diluting the obtained filtrate 1000 times is measured with a UV-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) using a 1 cm cell, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent has a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It can be evaluated that it is a solvent (slightly soluble solvent).

  Further, in the above evaluation method, an absorption spectrum is measured in the same manner as described above without diluting the obtained filtrate, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent can be evaluated as a solvent that does not substantially dissolve the coloring material represented by the general formula (I).

  The solvent having a solubility of the coloring material at 23 ° C. of 0.1 (mg / 10 g solvent) or less may be a solvent that does not substantially dissolve the coloring material represented by the general formula (I) or a hardly soluble solvent. There is no particular limitation, and it does not react with each component in the colorant dispersion, and may be appropriately selected from solvents that can be dissolved or dispersed.

In the colorant dispersion of the present invention, it is particularly preferable to use an ester solvent from the viewpoint of dispersion stability.
Examples of ester solvents include ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, Examples include 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate.

These solvents may be used alone or in combination of two or more.
The color material dispersion of the present invention is prepared by using the solvent as described above usually at a ratio of 60 to 85% by mass with respect to the total amount of the color material dispersion containing the solvent. When there are too few solvents, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, a coloring material density | concentration will fall and it may be difficult to achieve the chromaticity coordinate which makes a resin composition the target after preparation.

  In the color material dispersion of the present invention, the content of the color material is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the color material is preferably 5 to 40% by mass, and more preferably 10 to 20% by mass, based on the total amount of the color material dispersion.

(Other ingredients)
If necessary, the colorant dispersion of the present invention may further contain pigments, dyes, dispersion auxiliary resins, and other components.
The pigment and the dye are blended as necessary for the purpose of controlling the color tone. Conventionally known pigments and dyes can be selected according to the purpose, and can be used singly or in combination of two or more. The blending amount of the pigment and the dye is not particularly limited as long as the effect of the present invention is not impaired, and can be the same as that used in the color resin composition for color filter described later.
Examples of the dispersion auxiliary resin include alkali-soluble resins exemplified by a colored resin composition for color filter described later. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

<Method for producing colorant dispersion>
The colorant dispersion of the present invention is prepared by mixing and stirring the dispersant in a solvent to prepare a dispersant solution, and then mixing the colorant and other compounds as necessary in the dispersant solution. It can be prepared by dispersing using. The color material dispersion of the present invention may be prepared by mixing a color material and a dispersant in a solvent and dispersing the mixture using a known disperser.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibrating ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.

  Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a 0.1-0.5 micrometer membrane filter after dispersion | distribution.

  In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. However, the color material represented by the general formula (I) is refined to achieve high transmittance. , It is preferably set to 5 to 40 hours.

The average dispersed particle diameter of the color material in the color material dispersion is not particularly limited as long as it can produce a desired color when used as a color layer of a color filter, and improves contrast and heat resistance. From the point which is excellent in it, it is preferable to exist in the range of 10-150 nm, and it is more preferable to exist in the range of 20-125 nm. When the average dispersed particle diameter of the colorant is within the above range, the liquid crystal display device and the organic light emitting display device manufactured using the colored resin composition for a color filter of the present invention have high contrast and high quality. can do.
The average dispersed particle size of the color material in the color material dispersion is a dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. The particle size can be measured with a laser light scattering particle size distribution meter by appropriately diluting the color material dispersion liquid to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, a track particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.

  In this way, a color material dispersion excellent in dispersibility of the color material particles is obtained. The color material dispersion is used as a preliminary preparation for preparing a colored resin composition described later. That is, the color material dispersion is a ratio of (prepared color material in the composition) / (solid content other than the color material in the composition) in a pre-stage of preparing the colored resin composition described later. High colorant dispersion. Specifically, the ratio of (coloring material content in composition) / (solid content other than coloring material in composition) is usually 1.0 or more. By mixing the colorant dispersion and at least the binder component, a colored resin composition having excellent dispersibility can be prepared.

[Colored resin composition for color filter]
The colored resin composition for a color filter according to the present invention includes the color material dispersion according to the present invention, a binder component, and a solvent.

According to the present invention, by including the colorant dispersion according to the present invention, it is possible to achieve high contrast while achieving high brightness similar to that of dyes, and highly uniform colored resin composition for color filters. A colored layer having excellent heat resistance can be formed.
Further, when the colored resin composition for a color filter according to the present invention is a photosensitive resin composition described later, the developability is good. Usually, the cationic dye has a lower solubility in an alkaline aqueous solution during development due to electrostatic interaction between an acrylic acid group in an alkali-soluble resin described later and a cation of the dye. In particular, when it is uniformly dissolved in the resin composition, its influence is great, so the development solubility is poor. On the other hand, in the colored resin composition for a color filter according to the present invention, since the color material represented by the general formula (I) is dispersed by the dispersant, the dispersant covers the color material fine particles, and its steric hindrance. Therefore, the electrostatic interaction with the alkali-soluble acrylic acid group is eliminated, so that it is presumed to have sufficient development solubility.

The colored resin composition for a color filter of the present invention contains at least the colorant dispersion, a binder component and a solvent, and may contain other compounds as necessary.
Hereinafter, each component of the colored resin composition for a color filter of the present invention will be described in detail.
In addition, about the component which can be contained in the said color material dispersion liquid concerning the said invention, since the thing similar to what was demonstrated in the location of the said color material dispersion liquid can be used, description here is abbreviate | omitted.

(Binder component)
The colored resin composition for a color filter according to the present invention preferably contains a curable binder component in order to impart film formability and adhesion to the surface to be coated, and to impart sufficient hardness to the coating film. It does not specifically limit as a curable binder component, The curable binder component used in forming the coloring layer of a conventionally well-known color filter can be used suitably.
Examples of the curable binder component include a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains the thermosetting binder component to contain can be used.

When the colored resin composition for a color filter according to the present invention can be selectively adhered in a pattern on a substrate to form a colored layer, for example, when used in an ink jet system, the developability of the curable binder component Is not necessary. In this case, a known thermosetting binder component, a photosensitive binder component, or the like that is used when the color filter coloring layer is formed by an inkjet method or the like can be appropriately used.
As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, and an ethylenically unsaturated bond. An epoxy group is preferably used as the thermosetting functional group. Specific examples of the thermosetting binder component include those described in International Publication No. 2012/144521 pamphlet.

On the other hand, when using a photolithography process when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably.
Hereinafter, although the photosensitive binder component is demonstrated, a curable binder component is not limited to these.

(1) Photosensitive binder component Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include an alkali-soluble resin and a system containing an o-quinonediazide group-containing compound as a photosensitizing component, and examples of the alkali-soluble resin include a polyimide precursor.

  As the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used. Hereinafter, the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator will be described.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has a carboxyl group in the side chain, acts as a binder resin, and is suitably selected as long as it is soluble in a developer used for pattern formation, particularly preferably an alkali developer. Can be used.
A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an aromatic carbocyclic ring. The aromatic carbocycle functions as a component that imparts coating properties to the colored resin composition for color filters.
The acrylic copolymer having a carboxyl group may further contain a structural unit having an ester group. The structural unit having an ester group not only functions as a component that suppresses alkali solubility of the colored resin composition for a color filter, but also functions as a component that improves the solubility in a solvent and further the solvent resolubility.

Specific examples of the acrylic copolymer having a carboxyl group include those described in International Publication No. 2012/144521 pamphlet. Specifically, for example, methyl (meth) acrylate, ethyl ( Examples thereof include a copolymer composed of a monomer having no carboxyl group, such as (meth) acrylate, and one or more selected from (meth) acrylic acid and anhydrides thereof. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, when the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by mass, there is a tendency that the formed pattern is easily detached from the substrate or the pattern surface is roughened during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.
The epoxy compound, unsaturated group-containing monocarboxylic acid, and acid anhydride can be appropriately selected from known ones. Specific examples include those described in International Publication No. 2012/144521 pamphlet. Each of the epoxy compound, the unsaturated group-containing monocarboxylic acid, and the acid anhydride may be used alone or in combination of two or more.

  The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, but is preferably 1000 to 40000, more preferably 2000 to 5000.

  The alkali-soluble resin used in the colored resin composition for a color filter of the present invention may be used singly or in combination of two or more, and the content thereof is a colored resin composition for a color filter. Is usually in the range of 10 to 1000 parts by mass, preferably in the range of 20 to 500 parts by mass with respect to 100 parts by mass of the coloring material contained in the colorant. If the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained, and if the content of the alkali-soluble resin is too large, the ratio of the coloring material is relatively low, which is sufficient. The coloring density may not be obtained.

<Multifunctional monomer>
The polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator to be described later, and usually 2 ethylenically unsaturated double bonds are present. A compound having two or more is used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.
Such polyfunctional (meth) acrylate may be appropriately selected from conventionally known ones. Specific examples include those described in International Publication No. 2012/144521 pamphlet.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. Further, when the colored resin composition for a color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three (trifunctional) or more polymerizable double bonds. The poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid-modified products are preferred. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Succinic acid modification of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) Dipenta, succinic acid modified product of acrylate Risuri Tall hexa (meth) acrylate are preferable.
The content of the polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited, but is usually about 5 to 500 parts by weight, preferably about 100 parts by weight of the alkali-soluble resin. It is the range of 20-300 mass parts. If the content of the polyfunctional monomer is less than the above range, the photocuring may not sufficiently proceed and the exposed part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability is lowered. There is a risk.

<Photoinitiator>
There is no restriction | limiting in particular as a photoinitiator used in the colored resin composition for color filters of this invention, From the various photoinitiators known conventionally, it can use 1 type or in combination of 2 or more types. . Specific examples include those described in International Publication No. 2012/144521 pamphlet.

  The content of the photoinitiator used in the colored resin composition for a color filter of the present invention is usually about 0.01 to 100 parts by mass, preferably 5 to 60 parts by mass with respect to 100 parts by mass of the polyfunctional monomer. It is. If the content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the color layer may not have sufficient hardness. In some cases, the content of the coloring material or the like in the solid content of the composition is relatively reduced, and a sufficient coloring density cannot be obtained.

(Optional additive)
The colored resin composition for a color filter of the present invention may contain a pigment and various additives as necessary within a range that does not impair the object of the present invention.

(Pigment)
The pigment is blended as necessary for the purpose of controlling the color tone. Conventionally known pigments can be selected according to the purpose, and one or more pigments can be used.
Examples of the pigment include C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38; C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. And CI Pigment Blue 60.

  The blending amount of the pigment is not particularly limited as long as the effect of the present invention is not impaired. As the blending amount of the pigment, for example, the mass ratio of the colorant represented by the general formula (I) and the pigment is preferably 9: 1 to 4: 6, and 8: 2 to 5: 5. Is more preferable, and 7: 3 to 5: 5 is particularly preferable. This is because, within this range, the color tone can be controlled without impairing the high transmittance characteristic of the color material represented by the general formula (I).

(Additive)
Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Specific examples of the surfactant and the plasticizer include those described in International Publication No. 2012/144521 pamphlet.

(Mixing ratio of each component in the colored resin composition for color filter)
The total content of the colorant represented by the general formula (I) and the pigment blended as necessary is preferably 5 to 65% by mass with respect to the total solid content of the colored resin composition for color filters, more preferably Is preferably blended at a rate of 8 to 55% by mass. If the amount of the color material is too small, the transmission density when the colored resin composition for a color filter is applied to a predetermined film thickness (usually 1.0 to 5.0 μm) may not be sufficient, and there are many color materials. If it is too high, adhesion to the substrate when the colored resin composition for a color filter is applied and cured on the substrate, surface roughness of the cured film, coating film hardness, etc. may be insufficient. In addition, since the ratio of the amount of the dispersant used for dispersing the coloring material in the colored resin composition for the color filter is increased, there is a possibility that characteristics such as solvent resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Further, the content of the dispersant is not particularly limited as long as the colorant can be uniformly dispersed. For example, 10 to 150 parts by mass with respect to 100 parts by mass of the colorant is used. it can. Furthermore, it is preferable to mix | blend in the ratio of 15-45 mass parts with respect to 100 mass parts of coloring materials, and it is preferable to mix | blend especially in the ratio of 15-40 mass parts. The total content of the dispersant is preferably in the range of 1 to 60% by mass, particularly in the range of 5 to 50% by mass, based on the total solid content of the colored resin composition for color filters. It is preferable. When the content is less than 1% by mass relative to the total solid content of the colored resin composition for color filters, it may be difficult to uniformly disperse the color material, and exceeds 60% by mass. In some cases, the curability and developability may be reduced.
The total amount of the binder component is preferably 24 to 94% by mass, preferably 40 to 90% by mass, based on the total solid content of the colored resin composition for color filters.
Further, the content of the solvent is not particularly limited as long as the colored layer can be accurately formed. Usually, it is preferably in the range of 65 to 95% by mass, more preferably in the range of 75 to 88% by mass, based on the total amount of the colored resin composition for color filter containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

(Manufacture of colored resin composition for color filter)
As a method for producing a colored resin composition for a color filter, for example, (1) Into a solvent, the color material dispersion according to the present invention, a binder component, and various additive components used as desired are simultaneously added and mixed. And (2) a method in which a binder component and various additive components used as desired are added and mixed in a solvent, and then the colorant dispersion according to the present invention is added to and mixed with the binder component. Can be mentioned.

Next, the color filter of the present invention will be described.
[Color filter]
The color filter of the present invention is a color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers comprises the colored resin composition for a color filter of the present invention. It is a colored layer formed by curing.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed by curing using the above-described colored resin composition for a color filter of the present invention. Usually, a transparent substrate described later is used. It is formed in the opening part of the upper light-shielding part, and is usually composed of a coloring pattern of three or more colors.
In addition, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, the solid content concentration, the viscosity, and the like of the colored resin composition for a color filter, but is usually preferably in the range of 1 to 5 μm.

When the colored layer is, for example, a photosensitive resin composition, it can be formed by the following method.
First, the above-described colored resin composition for a color filter of the present invention is applied onto a transparent substrate described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. To form a wet paint film.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. A coating film of a colored resin composition for a color filter is used. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition for the color filter to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition for color filter is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

  Moreover, when forming the said colored layer by an inkjet system, it can be set as a conventionally well-known method, such as the method as described in the international publication 2012/144521 pamphlet, for example.

The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate to be described later, and can be the same as that used as a light shielding part in a general color filter.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used.
Specific examples of the light shielding part and the transparent substrate may be those described in International Publication No. 2012/144521 pamphlet, for example.
In addition, the color filter of this invention is not limited to the structure shown by FIG. 1, It can be set as a well-known structure as a color filter.

Next, the liquid crystal display device of the present invention will be described.
[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the above-described color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be a configuration generally known as a liquid crystal display device using a color filter. For the configuration of the liquid crystal display device and the method for forming the liquid crystal layer, for example, International Publication No. 2012/144521 can be referred to.

Next, the organic light emitting display device of the present invention will be described.
[Organic light emitting display]
The organic light emitting display device of the present invention includes the above-described color filter of the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view illustrating an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded onto the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitting body 80, known structures can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can generally have a known configuration as an organic light emitting display device using a color filter.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.

(Example 1: Synthesis of coloring material A)
(1) Synthesis of Intermediate A 5.0 g of p-phenylenediamine and 23.5 g of 1-iodonaphthalene were added to 200 mL of xylene, and 0.05 g of triphenylphosphine, 0.021 g of palladium acetate, sodium t-butoxide were added thereto. 12.5 g was added and refluxed for 5 hours before cooling. After completion of the reaction, water was added and extracted with chloroform. The organic layer was washed with water, concentrated and dried to obtain 14.4 g of intermediate A represented by the following chemical formula (1).

(2) Synthesis of Coloring Material A 10 g of Intermediate A and 6.2 g of Michler's ketone were added to 200 mL of toluene, and 3.8 g of phosphoryl chloride was added dropwise thereto, refluxed for 5 hours, and then cooled. After completion of the reaction, toluene was decanted. 100 mL of water was added and the resinous precipitate was filtered. The obtained cake was decomposed with dilute hydrochloric acid, filtered, washed with water, and dried to obtain 21.4 g of colorant A represented by the following chemical formula (2).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 489 (+), divalent and elemental analysis values: CHN measured value (77.75%, 7.50%, 7.98%); theoretical value (77.76%) 7.49%, 8.00%)

(Example 2: Synthesis of coloring material B)
Tokyo Chemical Industry Co., Ltd. 2,6-naphthalenedisulfonate-2sodium 1.03 g (3.10 mmol), methanol 30 mL, water 20 mL was added and stirred at 50-55 ° C. 3.33 g (3.10 mmol) of the coloring material A obtained in Example 1 was added, and the mixture was stirred at 50 to 55 ° C. for 1 hour. Methanol in the solution was concentrated with an evaporator, 100 mL of water was added, and the precipitate was collected by filtration and washed with water. The cake was dried to obtain 3.34 g (yield 95%) of coloring material B represented by the following chemical formula (3).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 489 (+), bivalent, 78 (-) divalent Elemental analysis values: CHN measured values (84.68%, 7.76%, 7.38%); Theoretical value (84.76%, 7.82%, 7.41%)

(Example 3: Synthesis of coloring material C)
In Example 2, instead of 2,6-naphthalenedisulfonate-2sodium, phosphotungstic acid n-hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O 7.07 g was used. In the same manner as in Example 2, a coloring material C represented by the following chemical formula (4) was obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 489 (+), divalent and elemental analysis values: CHN measured value (83.45%, 8.00%, 8.46%); theoretical value (83.47%) , 8.02%, 8.51%)

(Example 4: Synthesis of coloring material D)
(1) Synthesis of Intermediate B 1.30 g of 1,3,5-tribromobenzene and 8.59 g of 1-naphthylamine were added to 120 mL of xylene, and 0.15 g of triphenylphosphine, 0.068 g of palladium acetate, sodium After adding 8.07 g of t-butoxide and refluxing for 5 hours, the mixture was cooled. After completion of the reaction, water was added and extracted with chloroform. The organic layer was washed with water, concentrated and dried to obtain 7.52 g of intermediate B represented by the following chemical formula (5).

(2) Synthesis of coloring material D Intermediate B (6.0 g) and Michler's ketone (11.7 g) were added to toluene (200 mL), phosphoryl chloride (8.6 g) was added dropwise thereto, and the mixture was refluxed for 5 hours and then cooled. After completion of the reaction, toluene was decanted. 100 mL of water was added and the resinous precipitate was filtered. The obtained cake was decomposed with dilute hydrochloric acid, filtered, washed with water, and dried to obtain 10.5 g of a coloring material D represented by the following chemical formula (6).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 476 (+), trivalent element analysis value: CHN actual measurement value (77.36%, 7.53%, 8.22%); theoretical value (77.34%) 7.54%, 8.20%)

(Example 5: Synthesis of coloring material E)
Tokyo Chemical Industry Co., Ltd. 2,6-naphthalenedisulfonate-2sodium 1.03 g, methanol 30 mL, water 20 mL was added and stirred at 50-55 ° C. 3.18 g of the coloring material D obtained in Example 4 was added, and the mixture was stirred at 50 to 55 ° C. for 1 hour. Methanol in the solution was concentrated with an evaporator, 100 mL of water was added, and the precipitate was collected by filtration and washed with water. The cake was dried to obtain 3.10 g of a coloring material E represented by the following chemical formula (7).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 476 (+), trivalent, 78 (-) divalent Elemental analysis: CHN measured values (84.52%, 7.87%, 7.56%); Theoretical value (84.53%, 7.88%, 7.58%)

(Example 6: Synthesis of coloring material F)
In Example 5, instead of 2,6-naphthalenedisulfonate-2sodium, phosphotungstic acid n-hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O 7.08 g was used. In the same manner as in Example 5, a color material F represented by the following chemical formula (8) was obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 476 (+), trivalent elemental analysis value: CHN actual measurement value (83.20%, 8.09%, 8.70%); theoretical value (83.17%) , 8.10%, 8.73%)

(Comparative Example 1: Synthesis of coloring material G)
(1) Synthesis of Intermediate C Wako Pure Chemical Industries, Ltd. 1-iodonaphthalene 18.7 g, sodium tert-butoxide 9.88 g, Tokyo Kasei Co., Ltd. p-xylenediamine 5.0 g, Aldrich 2-dicyclohexyl Phosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 0.27 g, Wako Pure Chemical Industries, Ltd. 0.054 g of palladium acetate and xylene 36 mL were dispersed and reacted at 130-135 ° C. for 24 hours. After completion of the reaction, the mixture was cooled to room temperature and the precipitated crystals were filtered and washed with methanol. Subsequently, it was washed with water and dried to obtain 9.79 g of an intermediate C represented by the following chemical formula (9).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 389 (+),
Elemental analysis value: CHN actual measurement value (86.72%, 6.54%, 6.97%); theoretical value (86.56%, 6.23%, 7.21%)

(2) Synthesis of coloring material G Intermediate C 10.0 g, toluene 100 mL, and Wako Pure Chemical Industries, Ltd. phosphorus oxychloride 7.89 g were added and stirred. Next, 16.2 g of 4,4′-bis (diethylamino) benzophenone manufactured by Tokyo Chemical Industry was added, and the mixture was refluxed for 5 hours and cooled. After completion of the reaction, toluene was decanted. 100 mL of water was added and the resinous precipitate was filtered. The cake was dispersed with dilute hydrochloric acid, filtered, washed with water, and dried to obtain 18.4 g of a coloring material G represented by the following chemical formula (10).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 501 (+), divalent element analysis value: CHN measured value (78.02%, 7.13%, 7.11%); theoretical value (78.26%) , 7.32%, 7.82%)

(Comparative Example 2: Synthesis of coloring material H)
Tokyo Chemical Industry Co., Ltd. 2,6-naphthalenedisulfonate-2sodium 1.03 g, methanol 30 mL, water 20 mL was added and stirred at 50-55 ° C. 3.33 g of the coloring material G obtained in Comparative Example 1 was added, and the mixture was stirred at 50 to 55 ° C. for 1 hour. Methanol in the solution was concentrated with an evaporator, 100 mL of water was added, and the precipitate was collected by filtration and washed with water. The cake was dried to obtain 3.48 g of a coloring material H represented by the following chemical formula (11).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 502 (+), divalent, 78 (-) divalent Elemental analysis value: CHN measured value (84.77%, 8.01%, 7.29%); Theoretical value (84.78%, 7.98%, 7.23%)

(Comparative Example 3: Synthesis of Coloring Material I)
In Comparative Example 2, Comparative Example except that phosphotungstic acid n-hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O 7.07 g was used instead of 2,6-naphthalenedisulfonate-2sodium In the same manner as in Example 2, a coloring material I represented by the following chemical formula (12) was obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 502 (+), divalent, elemental analysis value: CHN measured value (83.50%, 8.19%, 8.22%); theoretical value (83.53% , 8.20%, 8.27%)

(Comparative Example 4: Synthesis of coloring material J)
(1) Synthesis of Intermediate 2 Wako Pure Chemical Industries, Ltd. 1-iodonaphthalene 15.2 g (60 mmol), Mitsui Chemicals, Inc. norbornanediamine (NBDA) (CAS No. 56602-77-8) 4.63 g , Sodium tert-butoxide 8.07 g, Aldrich 2-dicyclohexylphosphino-2 ′, 6 ′,-dimethoxybiphenyl 0.09 g, Wako Pure Chemical Industries, Ltd. palladium acetate 0.021 g, xylene 30 mL dispersed in 130 mL The reaction was allowed to proceed at −135 ° C. for 48 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted with water. Next, it was dried over magnesium sulfate and concentrated to obtain 8.5 g of intermediate 2 represented by the following chemical formula (13).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 407 (M + H),
Elemental analysis value: CHN actual measurement value (85.47%, 8.02%, 6.72%); theoretical value (85.26%, 8.11%, 6.63%)

(2) Synthesis of Color Material J Intermediate 2 8.46 g, Tokyo Chemical Industry 4,4′-bis (dimethylamino) benzophenone 13.5 g Toluene 60 mL was added and stirred at 45-50 ° C. 6.38 g of phosphorus oxychloride manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise, and the mixture was refluxed for 2 hours and cooled. After completion of the reaction, toluene was decanted. The resinous precipitate was dissolved by adding chloroform (40 mL), water (40 mL) and concentrated hydrochloric acid, and the chloroform layer was separated. The chloroform layer was washed with water, dried over magnesium sulfate and concentrated. 65 mL of ethyl acetate was added to the concentrate and refluxed. After cooling, the precipitate was filtered to obtain 15.9 g of colorant J represented by the following chemical formula (14).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent and elemental analysis values: CHN measured value (78.13%, 7.48%, 7.78%); theoretical value (78.06%) , 7.75%, 7.69%)

(Comparative Example 5: Synthesis of coloring material K)
Tokyo Chemical Industry Co., Ltd. 2,6-naphthalenedisulfonate-2sodium 1.03 g, methanol 30 mL, water 20 mL was added and stirred at 50-55 ° C. 3.39 g of the coloring material J obtained in Comparative Example 4 was added and stirred at 50 to 55 ° C. for 1 hour. Methanol in the solution was concentrated with an evaporator, 100 mL of water was added, and the precipitate was collected by filtration and washed with water. The cake was dried to obtain 3.40 g of a coloring material K represented by the following chemical formula (15).
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent, 78 (-) divalent Elemental analysis value: CHN measured value (84.35%, 8.42%, 7.20%); Theoretical value (84.50%, 8.37%, 7.12%)

(Comparative Example 6: Synthesis of coloring material L)
In Comparative Example 5, Comparative Example except that phosphotungstic acid n hydrate H ₃ [PW ₁₂ O ₄₀ ] · nH ₂ O 7.07 g was used instead of 2,6-naphthalenedisulfonate-2sodium In the same manner as in Example 5, a coloring material L represented by the following chemical formula (16) was obtained.
The obtained compound was confirmed to be the target compound from the following analysis results.
MS (ESI) (m / z): 511 (+), divalent,
Elemental analysis value: CHN actual measurement value (83.33%, 8.59%, 8.18%); theoretical value (83.23%, 8.64%, 8.13%)

<Heat resistance evaluation>
(1) Evaluation of thermal decomposition temperature About 5 mg of each of coloring materials A to L of Examples 1 to 6 and Comparative Examples 1 to 6 was put in a quartz pan, and a differential type differential thermal balance (TG) manufactured by Rigaku Corporation. -DTA) Using TG8120, a quartz pan was used as a reference for alumina, and the measurement was performed up to 800 ° C at a heating rate of 5 ° C / min. The extrapolated temperature of the peak of the obtained TG curve was taken as the decomposition point, and the temperature at the decomposition point was taken as the thermal decomposition temperature. The thermal decomposition temperature can be used as an index indicating heat resistance. The results are shown in Table 1.

(2) Evaluation of weight reduction rate About 5 mg of each of the colorants A to L of Examples 1 to 6 and Comparative Examples 1 to 6 was put in a quartz pan, and a differential type differential thermal balance (TG) manufactured by Rigaku Corporation. -DTA) Using TG8120, a quartz pan as a reference was heated to 230 ° C. with alumina at a temperature rising rate of 20 ° C./min, and kept at the same temperature for 60 minutes after reaching 230 ° C., and then the weight loss rate was measured. The weight reduction rate is calculated by the following formula and can be used as an index indicating heat resistance. The results are shown in Table 1.
Weight reduction rate = (weight before heating-weight after heating) / weight before heating x 100 (%)

[Summary of results]
From the results in Table 1, the following was clarified.
The color material A of Example 1 which is a color material represented by the general formula (I) has a higher thermal decomposition temperature than the color materials of Comparative Example 1 and Comparative Example 4 connected via sp ³ carbon. It was revealed that the weight reduction rate was low and the heat resistance was excellent.
The color material B of Example 2 having the same cation skeleton as the color material A of Example 1 but having different anions was also superior in heat resistance as compared with the color material of Comparative Example 2 and Comparative Example 5. Also, the color material C of Example 3 was superior in heat resistance as compared with Comparative Example 3 and Comparative Example 6.
Examples 2, 3, 5 and 6 using a divalent or higher anion were superior in heat resistance compared to Examples 1 and 4 using a monovalent anion.
The color material D of Example 4 having a trivalent cation is more excellent in heat resistance than the color material A of Example 1 which is a divalent cation, and is compared with the color materials of Comparative Example 1 and Comparative Example 4. And was excellent in heat resistance. Similarly, the color materials E and F of Examples 5 and 6 in which the anion skeleton was changed were also excellent in heat resistance as compared with Examples 2 and 3 which are divalent cations.

(Example 7: Preparation of colored resin composition 1)
(1) Preparation of coloring material dispersion 1 1.0 part by weight of coloring material B of Example 2 in a 30 ml mayonnaise bottle, Azizpar PB821 (manufactured by Ajinomoto Fine-Techno, poly having a repeating unit represented by the above general formula (i) Allylamine derivative) 0.6 parts by mass, propylene glycol monomethyl ether acetate (hereinafter PGMEA, manufactured by Daicel Chemical) 8.4 parts by mass, 2 mm in diameter of zirconia beads 2.0 parts by mass, and paint shaker (manufactured by Asada Steel) After preliminarily pulverizing for 1 hour, the solution was transferred to another 30 ml mayonnaise bottle, added with 2.0 parts by mass of zirconia beads having a diameter of 0.1 mm, and shaken in a paint shaker for 20 hours to obtain Colorant Dispersion Liquid 1 Obtained.

(2) Preparation of colored resin composition 1 3.31 parts by mass of the above colorant dispersion 1, a methacrylic acid / methyl methacrylate / benzyl methacrylate copolymer (molar ratio: 10/30/50, mass average molecular weight: 9000, acid value: 70 mg KOH / g, active ingredient content 40% by mass) 2.07 parts by mass, dipentaerythritol hexaacrylate monomer (“Aronix M-403” manufactured by Toa Gosei), 0.59 parts by mass, IRGACURE 907 (Ciba (Specialty Chemicals) 0.38 parts by mass, KAYACURE DETX-S (Nippon Kayaku) 0.08 parts by mass, KBM503 (Shin-Etsu Chemical) 0.03 parts by mass, Mega-Fac R08MH (by DIC) 0.0003 parts by mass , PGMEA 9.09 parts by mass, stirred and filtered through a 0.25 μm mesh, the colored resin of Example 7 It was obtained Narubutsu 1.

(Examples 8 to 10)
In Example 7, colored resin compositions 2 to 4 were obtained in the same manner as Example 7 except that the color materials C, E, and F were used instead of the color material B, respectively.

(Comparative Examples 7 to 10)
In Example 7, colored resin compositions 5 to 8 were obtained in the same manner as Example 7 except that the color materials H, I, K, and L were used instead of the color material A, respectively.

<Evaluation of heat resistance of coating film>
The colored resin compositions of Examples 7 to 10 and Comparative Examples 7 to 10 were each spin-coated on a glass substrate at 700 rpm for 5 seconds and dried on an 80 ° C. hot plate for 3 minutes.
This substrate was exposed with a UI-501C ultrahigh pressure mercury lamp manufactured by Ushio Corp. in a gap of 150 μm in the air. The exposure amount was 100 mJ / cm ^{2 as} measured by Ushio Corporation integrated light meter UIT-102 and photoreceiver UVD-365PD. The chromaticity of the obtained coating film was measured using a microspectroscope OSP-SP200 manufactured by Olympus Corporation.
Subsequently, the obtained coating film was heated at 230 degrees for 30 minutes, and the chromaticity was measured again, and the color difference ΔEab before and after the heating was calculated. The smaller the color difference, the better the heat resistance. The results are shown in Table 2.

[Summary of results]
From the results in Table 2, the following was clarified.
The colored resin composition 1 of Example 7 using the color material B which is the color material represented by the general formula (I) is a comparative example using the color material H and the color material K connected via sp ³ carbon. As compared with the colored resin compositions of No. 7 and Comparative Example 9, it was revealed that the obtained coating film was excellent in heat resistance.
The coloring resin composition 2 of Example 8 having the same color material B and cationic skeleton and using the coloring material C is also similar to the coloring resin compositions of Comparative Examples 8 and 10 using the coloring material I and the coloring material L. Compared to heat resistance.
The resin composition 3 of Example 9 using the coloring material E having a trivalent cation is more excellent in heat resistance than Example 7 using the coloring material B which is a divalent cation. Comparative Example 8 And better heat resistance than Comparative Example 10. Similarly, Example 10 using the colorant F having a changed anion skeleton was superior in heat resistance to Comparative Example 8 and Comparative Example 10.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electron injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (8)

A coloring material represented by the following general formula (I).
(In general formula (I), A represents an a-valent aromatic group, B ^c- represents a c-valent anion. R ^{1 to} R ⁵ each independently have a hydrogen atom or a substituent. R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring structure, and Ar ¹ has a substituent. And a plurality of R ^{1 to} R ⁵ and Ar ¹ may be the same or different from each other.
a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. ) A colorant dispersion liquid comprising a colorant represented by the following general formula (I), a dispersant, and a solvent having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less.
(In general formula (I), A represents an a-valent aromatic group, B ^c- represents a c-valent anion. R ^{1 to} R ⁵ each independently have a hydrogen atom or a substituent. R ² and R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring structure, and Ar ¹ has a substituent. And a plurality of R ^{1 to} R ⁵ and Ar ¹ may be the same or different from each other.
a represents an integer of 2 or more, and b, c, and d represent an integer of 1 or more. e is 0 or 1, and when e is 0, there is no bond. A plurality of e may be the same or different. )   The colorant dispersion according to claim 2, wherein the solvent is an ester solvent.   The colorant dispersion according to claim 2 or 3, wherein the dispersant is a polymer dispersant containing a nitrogen atom in the main chain or side chain.   A colored resin composition for a color filter, comprising the colorant dispersion according to any one of claims 2 to 4 and a binder component.   A color filter comprising at least a transparent substrate and a colored layer provided on the transparent substrate, wherein at least one of the colored layers is formed by curing the colored resin composition for a color filter according to claim 5. A color filter characterized by having a colored layer.   A liquid crystal display device comprising: the color filter according to claim 6; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.   An organic light emitting display device comprising the color filter according to claim 6 and an organic light emitter.