JP5611099B2 - Blue coloring composition for color filter, and color filter - Google Patents

Description

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

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

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

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

Therefore, in order to increase solubility and improve heat resistance and light resistance, color filters using a salt of an anionic dye and a cationic surfactant as a colorant have been proposed (for example, Patent Documents 2 and 3). reference). Generally, it is known that the solubility of an anionic dye in an organic solvent is increased by changing the sodium sulfonate group (—SO ₃ Na) of the anionic dye into an organic amine salt. In the above colorants, by changing the sodium sulfonate group of the anionic dye to the base salt of the cationic surfactant, the solubility of the anionic dye in the organic solvent is increased and the molecular weight is increased to increase the heat resistance. , Improve light resistance. However, in these methods, sufficient solubility with respect to the solvent used at the time of color filter production cannot be obtained, and the compatibility with the resin is poor, so the long-term storage stability of the color filter coloring composition, It has been difficult to provide strong adhesion between the coating film and a transparent substrate such as glass.

  Further, as salt forming compounds of anionic dyes, those using a cationic resin as a counter have been studied as crystalline aqueous coloring materials (see, for example, Patent Document 4). In color filter applications that require use in a dissolved state, detailed studies have not been made.

  On the other hand, a colored resin composition in which an anionic dye is added to a copolymer solution obtained by copolymerizing a monomer having an amide structure has also been proposed (see, for example, Patent Document 5). This is because the amide structure acts as a dyeing point with the anionic dye, thereby stabilizing the dye in the coating film and improving the resistance. However, the method disclosed here has a problem in that since a copolymer and an anionic dye are mixed in an organic solvent, a highly polar dye is not sufficiently dissolved and foreign matter is generated.

  However, the coloring composition using these dyes is not sufficient in heat resistance and light resistance, and indium tin oxide (ITO) for providing conductivity on the resist pattern of the color filter, particularly depending on the display method of the color liquid crystal display device. However, the presence of the ITO film also causes a problem that the heat resistance of the color filter using the dye is deteriorated.

JP-A-6-75375 JP-A-5-333207 JP 2004-307391 A JP-A-2005-350648 JP 2000-352819 A

  An object of the present invention is to provide a blue coloring composition for a color filter excellent in heat resistance, and a color filter excellent in color characteristics using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that a phthalocyanine blue pigment (A1) and a salt-forming compound of a xanthene acid dye having a specific structure (A2) have a molecular weight of 500 or less. And a blue colored composition for a color filter containing an epoxy group-containing compound having 3 to 5 functional groups is found to have excellent heat resistance, and the present invention has been made based on this finding. .

That is, the present invention includes a colorant (A), a binder resin (B), an epoxy group-containing compound (C), a photopolymerizable monomer (D), a photopolymerization initiator (E), and an organic material. A blue coloring composition for a color filter comprising a solvent, wherein the colorant (A) comprises a phthalocyanine blue pigment (A1) and a xanthene acid dye and a structural unit represented by the general formula (1) It contains a salt-forming compound (A2) obtained by reacting with a resin, and the epoxy group-containing compound (C) is an epoxy group-containing compound having a molecular weight of 500 or less and having 3 to 5 functional groups. The present invention relates to a blue coloring composition for a color filter.
General formula (1)

［一般式（１）中、Ｒ₁は水素原子、または置換もしくは無置換のアルキル基を表す。Ｒ₂〜Ｒ₄ は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、または置換されていてもよいアリール基を表し、Ｒ₂〜Ｒ₄のうち２つが互いに結合して環を形成しても良い。Ｑはアルキレン基、アリーレン基、―ＣＯＮＨ−Ｒ₅−、―ＣＯＯ−Ｒ₅−を表し、Ｒ₅はアルキレン基を表す。Ｙ^-は無機または有機のアニオンを表す。］

[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

In the present invention, the phthalocyanine blue pigment (A1) is C.I. I. It is related with the said blue coloring composition for color filters which is pigment blue 15: 6.
In the present invention, the xanthene acid dye is C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, and C.I. I. The present invention relates to the blue coloring composition for a color filter, which is any one selected from the group consisting of Acid Red 388.

  In the color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, the blue filter segment is formed of the blue coloring composition for the color filter. It relates to a color filter.

  According to the present invention, a color filter and a liquid crystal display device excellent in heat resistance can be obtained.

Hereinafter, the present invention will be described in detail.
In addition, "CI" mentioned below means a color index (CI), and when it shows either or both of "acryl, methacryl" in this specification, "(meth) acryl", May be described. Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

First, the blue coloring composition which concerns on one form of this invention is demonstrated.
A blue coloring composition according to an embodiment of the present invention is obtained by reacting a phthalocyanine blue pigment (A1) and a xanthene acid dye with a vinyl resin containing a structural unit represented by the general formula (1). An epoxy group-containing compound comprising a colorant (A) containing a salt-forming compound (A2), a binder resin (B), and an epoxy group-containing compound having a molecular weight of 500 or less and having 3 to 5 functional groups. C), a photopolymerizable monomer (D), a photopolymerization initiator (E), and an organic solvent.

<Colorant (A)>
The colorant (A) in the present invention is a salt-forming compound obtained by reacting a phthalocyanine blue pigment (A1) and a xanthene acid dye with a vinyl resin containing a structural unit represented by the general formula (1) (A2) is contained.

[Phthalocyanine blue pigment (A1)]
Examples of the phthalocyanine blue pigment (A1) constituting the colorant (A) used in the present invention include metal phthalocyanines having a central metal or metal-free phthalocyanine blue pigments, which can be produced by a known method. When using phthalocyanine blue pigments with copper, zinc, nickel or cobalt as the central metal, or metal-free phthalocyanine blue pigments, copper, zinc, nickel, An ε-type metal phthalocyanine pigment having cobalt as a central metal or a metal-free ε-type phthalocyanine pigment is obtained.

  Especially, it is preferable to use a copper phthalocyanine blue pigment as the phthalocyanine blue pigment (A1) in the present invention.

  Examples of the copper phthalocyanine blue pigment include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, and the like. Among them, copper phthalocyanine blue pigment having an ε-type structure is preferable. Such preferred pigments are specifically C.I. I. Pigment Blue 15: 6.

  The pigment is preferably used after being refined by a known method from the viewpoint of colorability, dispersibility, and contrast ratio.

  In addition to the colorant components, other organic pigments can be added to the blue coloring composition of the present invention in order to adjust brightness and hue.

[Salt-forming compound (A2)]
The salt-forming compound (A) is a compound obtained by reacting a xanthene acid dye with a vinyl resin containing a structural unit represented by the general formula (1).

(Xanthene acid dyes)
The xanthene-based acid dye has a red or purple color and has a dye form. A red or purple color means C.I. I. Acid Red, C.I. I. Acid dyes such as Acid Violet, C.I. I. Direct Red, C.I. I. It belongs to direct dyes such as direct violet. Here, since the direct dye has a sulfonic acid group, it is regarded as synonymous with an acid dye in the present invention.

  The salt-forming compound (A) is salted with these xanthene acid dyes (including direct dyes) and a vinyl resin containing a structural unit represented by the general formula (1) which is a counter component that works as a counter ion. It belongs to a modified salt-forming dye.

Specific acid dyes for xanthene dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (Edible Red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (edible red No. 5), Acid Rhodamine G, C.I. I. Acid Violet 9, C.I. I. Acid Violet 9, C.I. I. It is preferable to use Acid Violet 30.
Among them, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. It is preferable to use Acid Red 388 in terms of resistance and color characteristics.

As the xanthene acid dye, a rhodamine acid dye is preferably used in terms of excellent color developability.
In particular, as a xanthene acid dye, C.I. I. Acid Red 289, C.I. I. By using Acid Red 52, it is excellent in solvent solubility, and when used in combination with a blue pigment, it has excellent heat resistance, light resistance, and solvent resistance.

  In the transmission spectrum, the xanthene acid dye used in the present invention has a transmittance of 90% or more in the region of 650 nm, a transmittance of 75% or more in the region of 600 nm, a transmittance of 5% or less in 550 nm, and a region of 400 nm. Those having a transmittance of 70% or more are preferred. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance of 550 nm is 10% or less, and the transmittance is 75% or more in the region of 400 nm.

(Vinyl resin containing the structural unit represented by the general formula (1))
The counter constituting the salt-forming compound (A) used in the present invention is a vinyl resin containing a structural unit represented by the following general formula (1).

［一般式（１）中、Ｒ₁は水素原子、または置換もしくは無置換のアルキル基を表す。Ｒ₂〜Ｒ₄ は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、または置換されていてもよいアリール基を表し、Ｒ₂〜Ｒ₄のうち２つが互いに結合して環を形成しても良い。Ｑはアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ₅−、−ＣＯＯ−Ｒ₅−を表し、Ｒ₅はアルキレン基を表す。Ｙ^-は無機または有機のアニオンを表す。］

[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, R ₁ is most preferably a hydrogen atom or a methyl group.

In general formula (1), R _{2 to} R ₄ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Can be mentioned.

Here, as the alkyl group in R _{2 to} R ₄ , for example, a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n -Tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3) -Tetramethylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and pinanyl etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R _{2 to} R ₄ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R _{2 to} R ₄ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group, or aryl group represented by R _{2 to} R ₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R _{2 to} R ₄ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

_Two of R _{2 to} R ₄ may be bonded to each other to form a ring.

In general formula (1), the component of Q connecting the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group, Among these, —CONH—R ₅ — and —COO—R ₅ — are preferable because of polymerizability and availability. R ₅ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component Y ⁻ in the general formula (1) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  In order to obtain a vinyl resin containing a structural unit represented by the general formula (1) which is a preferred embodiment of the present invention, only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium group as a monomer component is used. Alternatively, after obtaining an acrylic resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, it may be obtained by a method in which an onium chlorinating agent is reacted and ammonium salified. good.

  Below, the specific example of the ethylenically unsaturated monomer which can be used in order to obtain the vinyl resin containing the structural unit represented by General formula (1) is shown.

  When copolymerizing an ethylenically unsaturated monomer having an ammonium group as a monomer component, examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, ( Alkyl (meth) acrylate quaternary ammonium salts such as (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyl Trimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl ammonium Alkyl (meth) acryloyl amide quaternary ammonium salts such as chloride, dimethyl diallyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  After obtaining an acrylic resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, when an onium chlorinating agent is reacted for ammonium chloride, the ethylenic group having an amino group Examples of the unsaturated monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, Diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, di (Meth) acrylic acid ester having a dialkylamino group such as sopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl (meth) acrylamide or ( Meth) acrylamides, styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylamine compounds such as diallylmethylamine and diallylamine, N-vinylpyrrolidine, N-vinylpyrrolidone, N-vinylcarbazole and the like And amino group-containing aromatic vinyl monomers.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the amino group and the onium chlorinating agent can usually be carried out by dropping an equimolar or less onium chlorinating agent with respect to the amino group into the ethylenically unsaturated monomer solution having an amino group. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

Alternatively, an alkoxycarbonylalkyl halide can also be used as the onium chlorinating agent. The alkoxycarbonylalkyl halide is represented by the following general formula (2).
General formula (2)

Z-R ₆ -COOR ₇

[In General Formula (2), Z is a halogen such as chlorine or bromine, preferably bromine, and R ₆ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. R ₇ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. ]
Reaction of the ethylenically unsaturated monomer and alkoxycarbonylalkyl halide with an amino group, after equimolar following alkoxycarbonylalkyl halide was reacted in the same manner as in the above onium chloride agent to an amino group, a -COOR ₇ It is obtained by hydrolysis and conversion to carboxylate ions (—COO ⁻ ). Thereby, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (2) and having an ammonium base can be obtained.

  Other examples of the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (1) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid. Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferable.

Specific examples of such vinyl monomers include the following compounds.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn -Butyl acryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  In addition, the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (1) may further include a copolymer unit derived from a monomer having an acid group.

  As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto Include mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

  Examples of the method for obtaining a vinyl resin containing the structural unit represented by the general formula (1) suitable for the present invention include anionic polymerization, living anion polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Any known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.
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(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) International Publication No. 96/030421 (Reference 6) International Publication No. 97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117 It is preferable to use an organic solvent. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

    The amount of ammonium base and amine base present in the vinyl resin containing the structural unit represented by the general formula (1) used in the present invention is the ammonium salt value of the resin, and the amine salt value is 10 to 200 mgKOH / g. It is preferably 20 to 130 mgKOH / g.

  If it is less than 10 mgKOH / g, the concentration of the pigment derived from the xanthene-based acidic dye is low, the resin component increases, and it does not function as a colorant component. Moreover, when it becomes larger than 200 mgKOH / g, a dye component will increase and solvent solubility will fall.

  Although the molecular weight of the vinyl resin containing the structural unit represented by the general formula (1) used in the present invention is not particularly limited, the converted weight average molecular weight measured by gel permeation chromatography (GPC). Is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  Moreover, it is preferable that the vinyl-type resin containing the structural unit represented by General formula (1) suitable for this invention has the characteristic melt | dissolved in the solvent widely used for the coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

  The total content of the structural unit represented by the general formula (1) is not particularly limited, but when the total structural unit contained in the vinyl resin is 100% by weight, From the viewpoint of coloring power, the total content of the structural unit represented by the general formula (1) is preferably 5% by weight or more, and more preferably 10 to 50% by weight.

(Salt formation)
The salt-forming compound (A) used in the present invention is prepared by stirring or vibrating an aqueous solution in which a vinyl-based resin containing a structural unit represented by the general formula (1) and a xanthene-based acidic dye are dissolved, or the general formula It can be easily obtained by mixing an aqueous solution of a vinyl resin containing the structural unit represented by (1) and an aqueous solution of a xanthene acid dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the xanthene acid dye are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the xanthene-based acidic dye is water-soluble and can be removed by washing with water. The vinyl-based resin and xanthene-based acidic dye to be used may each be a single type or a plurality of types having different structures.

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

  The content of the pigment component derived from the xanthene-based acidic dye in the salt-forming compound (A) can be adjusted to a range of 10 to 60% by weight, particularly 15 to 55% with respect to 100% by weight of the salt-forming compound (A). It is preferable to set it as the range of weight%. By controlling in this range, a salt-forming compound (A) excellent in solvent solubility can be obtained.

  Moreover, the weight% of the effective pigment component (excluding counter ions such as alkali metal ions) in the xanthene-based acidic dye contained in the salt-forming compound (A) is the same as the salt-forming compound (A) solution adjusted to the same concentration. It can be calculated by measuring the spectral spectrum of the xanthene acid dye solution and determining the spectral intensity ratio of the maximum absorption wavelength.

For example, using a solvent (such as N-methyl-2-pyrrolidone) that can well dissolve both the salt-forming compound (A) and the xanthene-based acid dye, the salt-forming compound (A) solution and the xanthene-based acid dye solution Is prepared at a certain concentration, and the absorbance at the maximum absorption wavelength of the salt-forming compound (A) solution and the xanthene-based acidic dye solution obtained by absorbance measurement is defined as Xa and Xb, respectively. Many xanthene acid dyes contain a counter ion such as an alkali metal ion. In this case, Na is the number of counter ions present in one molecule, and the atomic weight of the counter ion is Ma. When the molecular weight is Mb, the weight percentage of the effective pigment component in the xanthene acid dye is given by the following formula.
(1-Ma × Na / Mb) × 100 [wt%]
And using this formula, the weight% of the effective pigment component in the xanthene-based acidic dye contained in the salt-forming compound (A) can be calculated from the following formula.
(Xa / Xb) × (1-Ma × Na / Mb) × 100 [wt%]
The usage ratio of the blue pigment (A1) and the salt-forming compound (A2) is preferably 1 to 800 parts by weight of the salt-forming compound (A2) with respect to 100 parts by weight of the blue pigment (A1). More preferably, it is 2 to 400 parts by weight. If the addition amount of the salt-forming compound (A2) is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 800 parts by weight, the hue changes, which is not preferable.

  When converted in consideration of the color composition, the blending ratio of the blue pigment (A1) and the content of the effective pigment component in the xanthene-based acidic dye in the salt-forming compound (A2) is 100 parts by weight of the blue pigment (A1). On the other hand, the effective pigment component in the salt-forming compound (A2) is preferably 1 to 400 parts by weight. More preferably, the effective pigment component in the salt-forming compound (A2) is in the range of 2 to 300 parts by weight with respect to 100 parts by weight of the blue pigment (A1).

  In addition, the combination of the salt-forming compound (A2) with the blue pigment (A1) is favorable because it is adsorbed on the blue pigment while being dissolved and dispersed in the solvent.

<Binder resin (B)>
The binder resin (B) is one that disperses a colorant and one that stains and penetrates a salt-forming compound, and examples thereof include thermoplastic resins and thermosetting resins.
The binder resin (B) is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

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

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating foreign matter is generated after the salt-forming compound (A2) is applied. The stability of the salt-forming compound (A2) in the resist material is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the dye is not easily trapped in the resin and dye mixture, and the dye has a degree of freedom. The components tend to aggregate and precipitate, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the dye is easily trapped in the resin and dye mixture, Dye components are less likely to agglomerate and precipitate, and even when exposed to active energy rays to form a film, the resin is three-dimensionally cross-linked to fix the dye molecules, and the solvent can be removed in the subsequent development process. It is estimated that the dye component is less likely to aggregate and precipitate.

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

  When the binder resin (B) is used as a photosensitive coloring composition for a color filter, from the viewpoint of dispersibility, penetrability, developability, and heat resistance of the pigment and salt-forming compound, the colorant adsorbing group and during development The balance of the aliphatic group and aromatic group that act as affinity groups for the carboxyl group, colorant carrier and solvent of the pigment and salt-forming compound (A2), dispersibility, permeability, developability, Furthermore, it is important for durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin (B) is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant (A) because the film formability and various resistances are good, and the colorant concentration is high. From the standpoint of good color characteristics, it is preferably used in an amount of 1000 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin (B) include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. Is mentioned. Among them, it is preferable to use an acrylic resin.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.

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

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)
Acrylate is preferred.

As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro,
Examples thereof include monocarboxylic acids such as cyano-substituted products, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

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

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

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin (B) include epoxy resins, benzoguanamine resins, rosin-modified maleic resins, rosin-modified fumaric resins, melamine resins, urea resins, and phenol resins.

<Epoxy group-containing compound (C)>
The blue coloring composition of the present invention is excellent in heat resistance because the epoxy group-containing compound (C) contains an epoxy group-containing compound having a molecular weight of 500 or less and having 3 to 5 functional groups. Become. Preferably, the molecular weight is 50 to 500, more preferably 100 to 450.

  When the epoxy group-containing compound (C) is used to produce a color filter using the blue colored composition of the present invention, the epoxy group-containing compound (C) reacts at the time of firing the filter segment to increase the cross-linking density of the coating film, thereby improving the heat resistance of the filter segment. Conceivable. An epoxy group-containing compound having less than 3 functional groups does not have sufficient cross-linking density of the filter segment and is inferior in heat resistance. Even if the number of functional groups is 3 to 5, the epoxy group-containing compound having a molecular weight larger than 500 is similarly insufficient in crosslinking density and inferior in heat resistance. When the number of functional groups is 6 or more, the crosslink density is high, but the heat resistance is poor because the crosslink density in the filter segment is uneven depending on the location.

  The epoxy group-containing compound (C) of the present invention is not particularly limited as long as it is an epoxy group-containing compound having a molecular weight of 500 or less and having 3 to 5 functional groups. Moreover, since the epoxy group-containing compound is generally obtained as a mixture containing a plurality of by-products, the epoxy group-containing compound (C) of the present invention has a molecular weight of 500 or more or a functional group number other than 3 to 5 as a by-product. An epoxy group-containing compound having the number of functional groups may be included. The epoxy group-containing compound having a molecular weight of 500 or less and the number of functional groups of 3 to 5 is preferably 30% by weight or more based on the total amount of the epoxy group-containing compound (C) in the colored composition, and more preferably It is preferable to contain 50% by weight or more.

  Specific examples of the epoxy group-containing compound having a molecular weight of 500 or less and having 3 to 5 functional groups include low molecular weight epoxy group-containing compounds such as sorbitol tetraglycidyl ether and pentaerythritol tetraglycidyl ether. Examples of the product name of the epoxy group-containing compound of the present invention include EX-611 and EX-411 manufactured by Nagase ChemteX.

  The compounding amount of the epoxy group-containing compound (C) is a total amount including by-products, and is preferably 5.0 to 500 parts by weight with respect to 100 parts by weight of the dye in the salt-forming compound (A2). More preferably, it is -300 weight part. If it is less than 5.0 parts by weight, the heat resistance improving effect is not sufficient. When the amount is more than 500 parts by weight, a problem may occur when forming a filter segment by photolithography.

<Photopolymerizable monomer (D)>
The photopolymerizable monomer (D) that can be used in the present invention includes a monomer or an oligomer that is cured by ultraviolet rays or heat to produce a transparent resin. These may be used alone or in combination of two or more. Can be used. The blending amount of the photopolymerizable monomer (D) is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the total weight of the colorant (A), and is 10 to 10 from the viewpoint of photocurability and developability. More preferably, it is 400 parts by weight.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator (E)>
The blue colored composition for a color filter of the present invention is a solvent development type or alkali development type colored resist material by adding a photopolymerization initiator and the like in order to cure the composition by ultraviolet irradiation and form a filter segment by a photolithographic method. Adjust in the form of The blending amount of the photopolymerization initiator (E) is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the colorant (A), and is 5 to 400 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

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

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

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

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (E) contained in the colored composition, and is photocurable and developable. From the viewpoint, it is more preferably 5 to 50 parts by weight.

<Organic solvent>
The blue coloring composition of the present invention is obtained by sufficiently dispersing and infiltrating the colorant in the colorant carrier, and applying the filter segment on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. It contains a solvent to make it easier to form.

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

  Among them, since the dispersion and dissolution of the pigment of the present invention and the salt-forming compound (A) are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether It is preferable to use glycol acetates such as acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of health and safety and low viscosity.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When using 2 or more types of mixed solvents, it is preferable that said preferable organic solvent contains 65 to 95 weight% in 100 weight% of the whole organic solvent. In particular, propylene glycol monomethyl ether acetate is preferably the main component, and preferably 65 to 100% by weight in all organic solvents.

  Moreover, since the organic solvent can adjust a coloring composition to appropriate viscosity and can form the filter segment of the target uniform film thickness, it is the quantity of 800-4000 weight part with respect to 100 weight part of coloring agents (A). It is preferable to use it.

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

  As a particularly preferred leveling agent, it is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, has a hydrophilic group but has low solubility in water, and when added to a blue coloring composition, It has the feature that its surface tension lowering ability is low, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and the added amount that does not cause coating film defects due to foaming In this case, those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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

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

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

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

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

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

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant (A) in the blue coloring composition.

(Multifunctional thiol)
The blue coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as the polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator (E), a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation. Things become highly sensitive. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

  These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

  The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant (A). If the polyfunctional thiol content is less than 0.05 parts by weight, the effect of the chain transfer agent is small, and if it is more than 100 parts by weight, the polymerization initiating function is not improved, and developability, adhesion, etc. are insufficient. .

<The manufacturing method of a blue coloring composition>
The blue coloring composition of the present invention comprises a three-roll mill, a two-roll mill, a sand mill, a kneader, an atom and a blue pigment (A1) in a binder resin (B) and an organic solvent together with a pigment dispersant shown below as required. Obtained by stirring and mixing the pigment dispersion obtained by finely dispersing using various dispersing means such as a lighter and the salt-forming compound (A2) in the binder resin (B) and an organic solvent as necessary. In addition to the dye resin solution, an epoxy group-containing compound (C), a photopolymerizable monomer (D), a photopolymerization initiator (E), an organic solvent, and a binder resin (B) and additives as required Can be produced. In addition, the coloring composition containing two or more pigments can be produced by mixing finely dispersed pigments in a resin and a solvent separately, and can form a salt when the blue pigment (A1) is dispersed. The compound (A2) can be added and dispersed together for use.

<Pigment dispersant>
When dispersing the pigment, a pigment dispersant such as a surfactant, a resin-type pigment dispersant, and a dye derivative can be appropriately used. Since the pigment dispersant is excellent in dispersing the pigment and has a large effect of preventing re-aggregation of the pigment after dispersion, a colored composition obtained by dispersing the pigment in a resin and an organic solvent using the pigment dispersant was used. In this case, a color filter having excellent transparency can be obtained. The pigment dispersant can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

(Surfactant)
Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate. , Anionic surface activity such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Agents: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Nonionic surfactants such as ethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethyl Examples include alkylbetaines such as aminoacetic acid betaines, amphoteric surfactants such as alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Resin type pigment dispersant)
Resin-type pigment dispersants are resins that have a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the transparent resin, and stabilize the dispersion of the pigment into the transparent resin by adsorbing to the pigment. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 3184, manufactured by Japan Lubrizol Corporation 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400405, manufactured by Efka Chemicals 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 and the like.

(Dye derivative)
A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

<Removal of coarse particles>
The blue-colored composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more It is preferable to remove the dust.

<Color filter>
Next, a method for manufacturing the color filter of the present invention will be described.
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one blue filter segment is a blue coloring composition for the color filter of the present invention. It is formed using.

  The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  The red filter segment can be formed using a normal red coloring composition comprising a red pigment and a colorant carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, Red pigments such as 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Further, a basic dye or a salt-forming compound of an acid dye exhibiting a red color can also be used.

  The red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 , 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination. In addition, a salt forming compound of a basic dye or an acid dye that exhibits orange and / or yellow can be used.

The green filter segment can be formed using a conventional green coloring composition comprising a green pigment and a colorant carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used.
A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

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

<Color filter manufacturing method>
A color filter using the blue coloring composition of the present invention can be produced by a known method, but can be suitably produced by a photolithography method in particular.

  When the filter segment is formed by photolithography, the colored composition of the present invention is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. Apply to 5 μm. If necessary, the dried film is exposed to ultraviolet light or various lasers through a mask having a predetermined pattern provided in contact with or not in contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

  In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

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

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

  Moreover, the weight average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.

  The specific surface area of the pigment particles was determined by the BET method using nitrogen adsorption. For the measurement, an automatic vapor adsorption amount measuring device (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) was used.

  First, acrylic resin solutions (binder resin (B) component) used in Examples and Comparative Examples, fine pigments, vinyl resins containing a structural unit represented by the general formula (1), salt-forming compounds (A), It demonstrates from the manufacturing method of a pigment derivative, a pigment dispersion, and a salt-formation compound containing resin solution.

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

<Production method of fine pigment>
(Preparation of blue fine pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts, and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue fine pigment 1 were obtained. The specific surface area of the blue fine pigment 1 was 80 m ² / g.

<Method for Preparing Vinyl Resin Containing Structural Unit Represented by General Formula (1)>
(Preparation of vinyl resin 1)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a resin component having 47% by weight of an ammonium group was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

  Here, the weight average molecular weight (Mw) of the vinyl resin containing the structural unit represented by the general formula (1) was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

  The ammonium salt value of the vinyl resin containing the structural unit represented by the general formula (1) was determined by titrating with a 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator. It is the value converted into an equivalent and shows the ammonium salt value of solid content.

(Preparation of vinyl resin 2)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 2,2′-azobis (2,4-dimethylvaleronitrile 5.7) and 15.6 parts of methyl ethyl ketone were made uniform, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a vinyl resin 2 having a resin component of 40% by weight. The ammonium salt value of the obtained resin was 45 mgKOH / g.

<Method for Producing Salt-Forming Compound (A)>
(Salt-forming compound (A-1))
In the following procedure, C.I. I. A salt-forming compound (A-1) comprising Acid Red 289 and vinyl resin 1 in the side chain was produced.
51 parts of a vinyl resin was added to 2000 parts of water, and after sufficient stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise little by little to the resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A-1) of Acid Red 289 and vinyl resin 1 was obtained. At this time, C.I. in the salt-forming compound (A-1). I. The content of the effective pigment component derived from Acid Red 289 was 29% by weight.

(Salt-forming compound (A-2))
In the following procedure, C.I. I. A salt-forming compound (A-2) composed of Acid Red 289 and vinyl resin 2 was produced.
88 parts of vinyl-based resin 2 was added to 2000 parts of a 10% aqueous methanol solution, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise little by little to the resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 43 parts of C.I. I. A salt-forming compound (A-2) of Acid Red 289 and vinyl resin 2 was obtained. At this time, C.I. in the salt-forming compound (A-2). I. The content of the effective pigment component derived from Acid Red 289 was 22% by weight.

(Salt-forming compound (A-3))
In the following procedure, C.I. I. A salt-forming compound (A-3) comprising acid red 52 and vinyl resin 1 was produced.
51 parts of vinyl-based resin 1 was added to 2000 parts of water, and after sufficient stirring and mixing, the mixture was heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A-3) of acid red 52 and vinyl resin 1 was obtained. At this time, C.I. in the salt-forming compound (A-3). I. The content of the effective pigment component derived from Acid Red 52 was 30% by weight.

<Method for producing pigment derivative>
(Preparation of pigment derivative 1 (basic compound of copper phthalocyanine))
After adding 30 parts of copper phthalocyanine to 300 parts of chlorosulfonic acid and completely dissolving it, 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, then 15 parts of N, N-dimethylaminopropylamine was added, and the mixture was stirred at room temperature for 3 hours, then at 60 ° C. for 2 hours, filtered, washed with water and dried. 36 parts of a copper phthalocyanine sulfonic acid amide compound were obtained. The obtained copper phthalocyanine sulfonic acid amide compound was subjected to a composition analysis using a liquid chromatograph / mass spectrometer platform LCZ manufactured by Waters. It was a mixture of a copper phthalocyanine sulfonic acid amide compound having one group and a copper phthalocyanine sulfonic acid amide compound having two substituents of the following formula (3), and the weight ratio of each was 85:15. The obtained copper phthalocyanine sulfonic acid amide compound was designated as pigment derivative 1.

Formula (3)

<Method for producing blue pigment dispersion>
(Preparation of blue pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a blue pigment dispersion (DP-1) was obtained.

Blue fine pigment 1 (CI Pigment Blue 15: 6): 11.0 parts Dye derivative 1: 1.0 part Acrylic resin solution 1: 39.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan): 1.0 part

<Method for producing salt-forming compound-containing resin solution>
(Preparation of salt-forming compound-containing resin solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (DA-1).

Salt-forming compound (A-1): 12.0 parts Acrylic resin solution 1: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

  Hereinafter, the salt-forming compound-containing resin is the same as the salt-forming compound-containing resin solution (DA-1) except that the salt-forming compound (A-1) is changed to the salt-forming compound (A) shown in Table 1. A solution (DA-2, 3) was prepared.

[Examples 1-6, Comparative Examples 1-5]
After stirring and mixing the mixture of the blending amounts shown in Table 2 so as to be uniform, the mixture was filtered through a 1.0 μm filter to obtain a blue colored composition (alkali developing resist material (R-1 to 11)). .

Abbreviations in Table 2 are described below.
<Epoxy group-containing compound>
Epoxy compound 1: EX-611 (manufactured by Nagase ChemteX Corporation)
Epoxy compound 2: EX-411 (manufactured by Nagase ChemteX Corporation)
Epoxy compound 3: EHPE3150 (manufactured by Daicel Chemical Industries)
Epoxy compound 4: EX-201 (manufactured by Nagase ChemteX Corporation)
<Photopolymerizable monomer>
Photopolymerizable monomer 1: Trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
<Photopolymerization initiator>
Photopolymerization initiator 1: ("Irgacure 907" manufactured by Ciba Japan)
<Sensitizer>
Sensitizer 1: ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
<Solvent>
PGMAC: Propylene glycol monomethyl ether acetate

Table 3 shows the contents of the epoxy group-containing compound used.

(Evaluation of resist material)
The coating film heat resistance test of the coating film of the obtained resist material (R-1 to 11) was performed by the following method. Table 4 shows the test results.

(Method of coating heat resistance test)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and UV exposure is performed through a mask having a predetermined pattern, and then an alkali developer is sprayed to remove uncured portions. Thus, a desired pattern was formed. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. Thereafter, an ITO (indium tin oxide) film was formed by sputtering so as to have an average film thickness of 1500 mm. Using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source Measured. Further, as a heat resistance test, the sample was heated in an oven at 230 ° C. for 3 hours, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured color difference value, the color difference ΔEab * was calculated according to the following formula, and the heat resistance of the coating film was evaluated.
ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

＊１ レジスト材中のエポキシ化合物の割合（重量％）
青色着色組成物全量（１００重量％）中のエポキシ基含有化合物の含有量
＊２ 染料に対するエポキシ化合物の割合（重量部）
造塩化合物（Ａ２）中の染料１００重量部に対するエポキシ基含有化合物の含有量

* 1 Ratio of epoxy compound in resist material (wt%)
Content of epoxy group-containing compound in the total amount (100% by weight) of the blue coloring composition * 2 Ratio of epoxy compound to dye (parts by weight)
Content of epoxy group-containing compound with respect to 100 parts by weight of dye in salt-forming compound (A2)

  The blue coloring composition of the present invention comprising the phthalocyanine blue pigment (A1) and the salt-forming compound (A2) of the present invention and an epoxy group-containing compound having a molecular weight of 500 or less and a functional group number of 3 to 5, In all cases, ΔEab * was small and heat resistance was good.

  Further, when Examples 1 to 3 (resist materials R-1 to 3) differing only in the content of the epoxy group-containing compound (C) are compared, ΔEab * is smaller as the content of the epoxy group-containing compound (C) is larger. The heat resistance was good.

(Manufacture of color filters)
A total of 12.0 parts of the blue fine pigment 1 and the dye derivative 1 in the blue pigment dispersion (DP-1) is obtained from C.I. I. Pigment Red 254 / C.I. I. Pigment Red 177 = 7.2 parts / 4.8 parts, C.I. I. Pigment Green 36 / C.I. I. Pigment Yellow 150 = 7.2 parts / 4.8 parts except that the pigment dispersion was prepared in the same manner as the blue pigment dispersion (DP-1) except that the pigment dispersion was replaced with 4.8 parts. The total of the salt compound-containing resin solution was replaced with each color pigment dispersion to obtain a red coloring composition for a color filter and a green coloring composition for a color filter.

The red coloring composition was applied on a 100 mm × 100 mm glass substrate with a die coater to a thickness of about 2 μm, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate is washed with ion-exchanged water, and this substrate is heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. did. Next, by the same operation, a green filter segment is formed using a green coloring composition next to the red filter segment, and then a blue filter segment is formed using the resist material R-1, and three color filters are formed on the same glass substrate. A color filter having segments was obtained.

  When the blue coloring composition for color filters (resist material) in the present invention was used, a color filter having a blue filter segment having excellent color characteristics and good heat resistance in a wide chromaticity range could be produced.

Claims (4)

Color filter comprising a colorant (A), a binder resin (B), an epoxy group-containing compound (C), a photopolymerizable monomer (D), a photopolymerization initiator (E), and an organic solvent A blue coloring composition for
Salt Forming Compound (A2) Obtained by Reacting Colorant (A) with Phthalocyanine Blue Pigment (A1) and Xanthene Acid Dye and Vinyl Resin Containing Structural Unit Represented by General Formula (1) Containing
The blue coloring composition for color filters, wherein the epoxy group-containing compound (C) is an epoxy group-containing compound having a molecular weight of 500 or less and a functional group number of 3 to 5.
General formula (1)

[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]   The phthalocyanine blue pigment (A1) is C.I. I. The blue coloring composition for a color filter according to claim 1, which is CI Pigment Blue 15: 6.   Xanthene acid dyes are C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, and C.I. I. The blue coloring composition for a color filter according to claim 1 or 2, wherein the composition is any one selected from the group consisting of Acid Red 388.   The color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the blue filter segment is a blue coloring composition for a color filter according to any one of claims 1 to 3. A color filter formed by objects.