JP2012073291A - Colored composition for color filter, color filter using the same, and display device - Google Patents

Abstract

【選択図】なし[PROBLEMS] To provide a color filter that is not only electrochemically and thermally stable, but also has good solubility in organic solvents and resins, has excellent development solubility, and is resistant to NMP and has high electrical reliability. It is to provide a colored composition, a color filter using the same, and a display device.
A color composition for a color filter comprising a binder resin, a crosslinkable monomer, a photopolymerization initiator, a colorant and a solvent, wherein the colorant is a triarylmethane dye represented by the following general formula (I): It is a thing.

[Selection figure] None

Description

  The present invention relates to a coloring composition for a color filter, a color filter using the same, and a display device, and in particular, a coloring composition for a color filter having high heat resistance and light resistance and high adhesion of a colored layer to a substrate. The present invention relates to a color filter and a display device using the same.

A color filter may be used for a liquid crystal or an electroluminescence (EL) display device. The color filter has a structure in which a colored layer is laminated on a substrate, and the colored layer is required to have heat resistance and light resistance.
As a material used for the colored layer, an example using a triarylmethane dye and an aromatic sulfonic acid as a counter anion of the triarylmethane dye in order to improve durability to heat and light is known (for example, (See Patent Document 1 or 2).

Among them, in Patent Document 1, durability is improved by introducing a photopolymerizable functional group into an aromatic ring of an aromatic sulfonic acid and forming a chemical bond between the photopolymerizable resin and the crosslinkable monomer contained therein. More specifically, it has a triarylmethane dye monomer or a polymer obtained by polymerizing the dye monomer, an aromatic sulfonic acid having a photoreactive group as a counter anion, and a resin as a binder. A photosensitive coloring composition suitable for use in a color filter containing benzene has been proposed (see Patent Document 1). According to this photosensitive coloring composition, it is said that a photosensitive coloring composition for a color filter having excellent light resistance, heat resistance and transparency can be obtained (see Patent Document 1, Paragraph 0008).
However, triarylmethane dyes with aromatic sulfonic acid as the counter anion have a uniform ink composition due to poor solubility in ester solvents such as propylene glycol monomethyl ether acetate (PGMEA), acrylic acid resin and crosslinkable monomers. Even if it can be made into a solution, the dye precipitates in the coating film, which causes problems such as loss of the high permeability that is characteristic of the dye, and the specifications as a colorant for color filters are sufficient. Since it does not satisfy, it has not yet reached practical use.
Patent Document 2 describes a composition containing a colorant having a triarylmethane dye having a specific structure and an aromatic sulfonate ion as a counter anion, but has sufficient adhesion and light resistance to the substrate. It wasn't.

On the other hand, as a means for improving the durability of a cationic dye such as triarylmethane, Patent Document 3 discloses that an imido acid ion is used as a counter anion. The triarylmethane dye using imide acid as the counter anion exhibits high solubility in ester solvents such as PGMEA, acrylic acid resin and crosslinkable monomer, and gives a uniform coating film. In addition, the dye itself is superior in durability compared to a triarylmethane dye having an aromatic sulfonate ion as a counter anion, and is promising as a coloring dye for a color filter.
However, a composition in which a triarylmethane dye using imide acid is mixed with an acrylic acid resin, a crosslinkable monomer, a photopolymerization initiator, and a solvent has poor solvent resistance of the coating film, and has electrical reliability. There was a problem of being low.

  In addition, it has been proposed to introduce a metal alkoxide such as alkoxysilane in order to fix a dye or pigment in a coating film and obtain sufficient heat resistance (see, for example, Patent Documents 4 and 5). For example, in Patent Document 5, a pigment is included in a network structure of a polymer made of a metal-oxygen bond using a sol-gel method, or a polymer made of a metal-oxygen bond. It is said that the pigment is not eluted by an organic solvent or the like (see Patent Document 5, paragraph 0028).

  Further, a colorant for a color filter containing a binder polymer, a crosslinkable monomer, a photopolymerization initiator, a dye as a colorant, and a silane compound having a photocrosslinkable functional group and a reactive group that forms a siloxane bond by a dehydration polymerization reaction. A composition has been proposed (see Patent Document 6). This color filter colorant composition uses a dye as a colorant and is said to have excellent transparency and colorability and high durability (see Patent Document 6, paragraph 0004).

Japanese Patent No. 4266627 JP 2008-304766 A JP 2007-503477 A U.S. Pat. No. 4,948,843 JP-A-6-308314 JP 2000-47020 A

  As described above, in the coloring composition using the conventional triarylmethane dyes disclosed in Patent Documents 1 and 2, although heat resistance can be secured to some extent, light resistance is not sufficient, and in the plate making process, However, the exposure sensitivity is low, the curing is poor, and the development solubility is low.

  By the way, in a color filter used for a liquid crystal display, an alignment film is an essential component, and a polyimide film is often used as the alignment film. As the polyimide film, N-methylpyrrolidone (hereinafter abbreviated as “NMP”) is usually used as a solvent in the production process. When the polyimide film is used in contact with the color filter, the color filter is used. However, it is required to have resistance to NMP. Such a problem does not occur when a conventional pigment dispersion resist is used as a color filter. However, in a system using a dye, it is a very big problem that the dye has a property of eluting into NMP. Even when it is in contact with NMP, it is required that the dye is immobilized in the film.

Moreover, when using dye as a coloring material for liquid crystal color filters, it is calculated | required that the colored coating film has sufficient electrical reliability. The dye itself enters the liquid crystal layer and moves through the liquid crystal layer, thereby preventing the voltage applied to the liquid crystal layer from being held for a certain period. In particular, when an ionic dye such as an acid dye or a basic dye is used, the fact that the dye has a property of eluting into the liquid crystal layer results in a display failure of the color liquid crystal display device. Is required to be fixed.
The electrical reliability can be evaluated by the voltage holding ratio when a liquid crystal cell is produced using a curable coloring composition, and high electrical reliability means that the voltage holding ratio is high.

  The problems of NMP resistance and electrical reliability can be overcome by providing a protective layer directly on the colored coating film. However, since the protective layer is generally made of a photocurable or thermosetting organic resin, the solvent resistance to the solvent used when the solution is applied to the colored coating film is required at a minimum.

The cationic dye disclosed in Patent Document 3 described above cannot suppress the elution of the dye into a solvent or liquid crystal even when the resist is sufficiently cured, and also has poor resistance to a solution when forming a protective layer. Therefore, it cannot be used as a coloring composition for a color filter.
In addition, the cationic dye disclosed in Patent Documents 1 and 4 to 6 described above, in which a metal alkoxide such as alkoxysilane is introduced into the counter ion, has the dye immobilized in the film, and the dye flows out into the organic solvent. Although it is difficult to do so, the coloring composition using the sol-gel method described in Patent Documents 4 to 6 described above has a significantly low development solubility when patterned by an exposure-development process. It has been clarified by the present inventors that improvement is necessary.

That is, the present invention has been made to solve the above-described problems, and is not only electrochemically and thermally stable, but also has both good solubility in organic solvents and resins, and development. An object of the present invention is to provide a coloring composition for a color filter having excellent solubility and high resistance to NMP and high electrical reliability, and a color filter and a display device using the same.
Here, the development solubility means the development solubility of an unexposed portion in the exposure / development process.

As a result of intensive studies to solve the above-mentioned problems, the present inventor made the counter anion in the triarylmethane dye as a sulfonylimido ion into which a specific photoreactive group was introduced, while maintaining heat resistance. In addition to being able to achieve both solubility in organic solvents and resins and light resistance, it also improves resistance to solvents used when forming NMP and protective layers, such as CHXA (cyclohexanol acetate), and also has high electrical reliability. And the present invention was completed.
That is, the present invention
(1) A colored composition for a color filter comprising a binder resin, a crosslinkable monomer, a photopolymerization initiator, a colorant and a solvent, wherein the colorant is a triarylmethane dye represented by the following general formula (I) ,

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Any one of aryl groups, and any of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to form part of a ring structure or heterocyclic structure; X in the formula is an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, Y represents a divalent hydrocarbon group, and Z is a photoreactive group.)
(2) The coloring composition for a color filter according to the above (1), wherein Y in the general formula (I) is an arylene group,
(3) The color filter according to the above (1) or (2), wherein Z in the general formula (I) is a group selected from a vinyl group, an allyl group, a (meth) acryl group, and a (meth) acryloyl group. Coloring composition,
(4) The coloring composition for a color filter according to any one of (1) to (3), wherein X in the general formula (I) is a perfluoroalkyl group,
(5) In the above general formula (I), R ⁵ is a hydrogen atom, and R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms (1 ) To (4), a coloring composition for a color filter,
(6) The coloring composition for a color filter according to the above (5), wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are all the same.
(7) The coloring composition for a color filter according to any one of (1) to (6), further including a pigment,
(8) A color filter comprising at least a colored layer on the substrate, wherein the colored layer is formed using the colored composition for a color filter according to any one of (1) to (7), and (9) A liquid crystal display device comprising the color filter according to (8), a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate,
Is to provide.

  According to the present invention, while maintaining heat resistance, it is possible to achieve both solubility in organic solvents and resins and light resistance, and also has excellent resistance to solvents used during NMP and protective layer formation, and A coloring composition for a color filter having excellent electrical reliability, a color filter using the same, and a liquid crystal display device can be provided.

It is a schematic diagram which shows the liquid crystal display device of this invention.

Embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
<Coloring composition for color filter>
The coloring composition for a color filter of this embodiment includes a binder resin, a crosslinkable monomer, a photopolymerization initiator, a coloring agent, and a solvent, and the coloring agent is represented by the following general formula (I). It is characterized by being.

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Any one of aryl groups, and any of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to form part of a ring structure or heterocyclic structure; . In the formula, X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, Y represents a divalent hydrocarbon group, and Z represents a photoreactive group.

(Coloring agent)
First, the colorant in the present embodiment will be described.
The colorant in the present embodiment is a triarylmethane dye represented by the general formula (I), and examples of the alkyl group in the R ^{1 to} R ⁶ of the general formula (I) include a saturated alkyl group and an unsaturated alkyl group. And cycloalkyl groups, and these include substituents such as aryl groups, alkyloxy groups, aryloxy groups, acyloxy groups, halogen atoms, acylamino groups, alkyloxycarbonyl groups, aminocarbonyl groups, hydroxy groups, and cyano groups. You may have.
More specifically, the alkyl group may be a linear, branched or cyclic alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group, an n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, , 3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t -Octyl group, branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched heptadecyl group, branched Octadecyl group, linear or branched nonadecyl group, linear or branched eicosanyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group , Cyclooctyl group, cyclohexyl Propyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyl Preferred examples include an adamantyl group, a quinuclidinyl group, a cyclopentylethyl group, and a bicyclooctyl group.

Examples of the aryl group in R ^{1 to} R ⁶ include a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, an anthracenyl group, an anthraquinonyl group, a pyrenyl group, and a heterocyclic group. , Alkyloxy group, aryloxy group, halogen atom, nitro group, cyano group, hydroxy group, substituted carbamoyl group, substituted sulfamoyl group, substituted amino group, substituted oxycarbonyl group, substituted oxysulfonyl group, alkylthio group, arylsulfonyl group, And may have a substituent such as a phenyl group.

More specifically, for example, the substituted phenyl group includes an o-, m- or p-methylphenyl group, an o-, m- or p-ethylphenyl group, an o-, m- or p-propylphenyl group. , O-, m- or p-isopropylphenyl group, o-, m- or p-tert-butylphenyl group, o-, m- or p-aminophenyl group, o-, m- or p- (N, N-dimethylamino) phenyl group, o-, m- or p-nitrophenyl group, o-, m- or p-hydroxyphenyl group, o-, m- or p-methoxyphenyl group, o-, m- or p-ethoxyphenyl group, o-, m-, p- (trifluoromethyl) phenyl group, o-, m-, p- (trifluoromethoxy) phenyl, o-, m-, p- (trifluoro) Romethylsulfanyl) phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, o-, m- or p-iodo Examples include phenyl group, 3,4- or 3,5-dimethoxyphenyl, 5-fluoro-2-methylphenyl, 3,4,5-trimethoxyphenyl, 2,4,5-trimethylphenyl, and the like.
Further, for example, as an aryl group having an alkyl group as a substituent, a benzyl group, 4-methoxyphenylethyl group, 3-methoxyphenylethyl group, 2-methoxybenzyl group, 3-methoxybenzyl group, 4-methoxybenzyl group, 2-ethoxybenzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-tert-butylbenzyl group, 2- (trifluoromethyl) benzyl group, 3- (trifluoromethyl) benzyl group, 4-fluorobenzyl Group, 3-iodobenzyl group, 4- (trifluoromethoxy) benzyl group, 3- (trifluoromethoxy) benzyl group and 4- (trifluoromethylsulfanyl) benzyl group.

Further, in the general formula (I), any ^one of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ is bonded to form a part of a ring structure or a heterocyclic structure. Examples of the ring include piperidine, morpholine, pyrrolidine, piperazine, hexamethyleneimine and the like. Examples of the substituent represented by R ¹ R ² N—, R ³ R ⁴ N—, and R ⁵ R ⁶ N— include, for example, a pyrrolidino group, a piperazino group, a morpholino group, an N-ethylpiperazino group, Dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, N-ethyl-N-isobutylamino group, N-ethyl-benzylamino group, diamylamino group, dihexylamino group, dioctylamino group, N-ethyl-N -Tetrafurfurylamino group, dibenzylamino group, etc. are mentioned. Among these, a 5-membered ring and a 6-membered ring are preferable.

Among these, R ⁵ is a hydrogen atom, and R ¹ , R ² , R ³ , R ⁴ and R ⁶ are preferably each independently an alkyl group from the viewpoint of ease of dye production. Preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably an ethyl group and a methyl group.
Further, as described above, R ¹ , R ² , R ³ , R ⁴ and R ⁶ may be different or the same, but are preferably the same from the viewpoint of the dye structure.

On the other hand, in the sulfonylimido ion having a photoreactive group as a counter anion, as described above, X is an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, and Y is a divalent group. And Z is a photoreactive group.
Examples of the alkyl group constituting X include the same alkyl groups as those described above for R ^{1 to} R ^6, and a part of the hydrogen atoms may be substituted with fluorine atoms. In particular, a fluorinated alkyl group having 1 to 3 carbon atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms is preferred. Among them, a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms is an imide. This is particularly preferred from the viewpoint of increasing the acidity of the acid and improving the stability of the dye.
Specifically, for example, trifluoromethyl group, difluoromethyl group, fluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoro A propyl group, a 3-fluoropropyl group, etc. can be mentioned.

Next, there is no restriction | limiting in particular as a bivalent hydrocarbon group represented by Y, For example, a C1-C10 linear or branched alkylene group, a C6-C20 arylene group, C7-C7 And 20 arylalkylene groups. Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and various butylene groups. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the arylalkylene group include an arylmethylene group, an arylethylene group, and an arylpropylene group. Of these, an arylalkylene group having 7 to 10 carbon atoms is preferable from the viewpoint of availability of raw materials and production, and an arylmethylene group, an arylethylene group, and an arylpropylene group are particularly preferable.
The arylalkylene group includes an ortho form, a meta form and a para form, but is preferably a para form from the viewpoint of no steric hindrance.

In addition, examples of the photoreactive group represented by Z include those in which the reaction proceeds through a polymerization reaction such as photo radical polymerization, photo cation polymerization, or photo anion polymerization.
Examples of the radical photopolymerization reactive group include a functional group having an ethylenically unsaturated bond (preferably an ethylenic double bond). Specifically, a vinyl group, an allyl group, a (meth) acryl group, (Meth) acryloyl group, vinyl cycloalkyl group, etc. are mentioned. Among these, a vinyl group, an allyl group, a (meth) acryl group, and a (meth) acryloyl group are preferable from the viewpoints of photoreactivity and synthesis.
Moreover, as a photocationic polymerization reactive group, cyclic ether groups, such as an epoxy group and an oxetanyl group, a thioether group, and a vinyl ether group are mentioned, for example.

  Examples of the triarylmethane dye represented by the general formula (I) include compounds represented by the following exemplified compounds (1) to (3).

As in the exemplified compounds (1) to (3), R ⁵ in the general formula (I) is a hydrogen atom, and R ¹ , R ² , R ³ , R ⁴ and R ⁶ are the same alkyl group. Compounds are particularly preferred.

The triarylmethane dye represented by the general formula (I) can be synthesized by a known method. As a synthesis method, for example, the method described in “Review Review Synthetic Dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968) is useful.
Counter anion, a dye represented by the following formula, for example counter anion Cl ^- to the dye represented by the corresponding sulfonyl imide acid was added, can be synthesized by a salt exchange.

Specifically, the counter anion is Cl ^- to dissolve the dye represented by the reaction solvent, the corresponding sulfonyl imide acid was added and, after stirring, the precipitate can be synthesized by removing by filtration. The amount of sulfonylimide acid added is, for example, about 1 to 3 equivalents. Examples of the reaction solvent include water; alcohol solvents such as methanol, ethanol, and 2-propanol; or a mixed solvent thereof. The reaction temperature is preferably 0 ° C. to 40 ° C., for example.

  In addition to the triarylmethane dye represented by the general formula (I), the colorant may contain an organic pigment. Specific examples of organic pigments that can be used here include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. And violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38. Among them, C.I. I. Pigment red violet 23, C.I. I. Pigment Blue 15: 3, preferably containing at least one pigment selected from 15: 6, C.I. I. It is particularly preferable that pigment blue 15: 6 is contained. These pigments may be used alone or in combination of two or more.

The organic pigment is obtained by rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc., if necessary. Atomization treatment, cleaning treatment with an organic solvent or water for removing impurities, removal treatment with an ion exchange method of ionic impurities, or the like may be performed.
The organic pigment preferably has a uniform particle size. Moreover, the pigment dispersion liquid in the state in which the pigment is uniformly dispersed in the solution can be obtained by carrying out the dispersion treatment by containing the pigment dispersant.
Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants, which may be used alone or in combination of two or more. Good.

(Binder resin)
The binder resin used in the present embodiment is not particularly limited, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like. Moreover, it is preferable that it is alkali-soluble.
The alkali-soluble binder resin is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such a linear organic high molecular polymer include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid as described in Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Application Laid-Open No. 59-53836, Japanese Patent Application Laid-Open No. 59-71048 There are a copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and the like, and an acidic cellulose derivative having a carboxylic acid in the side chain is also useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

The alkali-soluble binder resin may be a copolymer of a hydrophilic monomer. Examples of the alkali-soluble binder resin include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and glycerol (meth) acrylate. (Meth) acrylamide, N-methylol acrylamide, secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, Methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) ) Acrylate, and the like.
Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salts, and monomers containing morpholinoethyl group. is there.

In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Although the example of the polymer containing these polymeric groups is shown below, if alkali-soluble groups, such as a COOH group, OH group, an ammonium group, and a carbon-carbon unsaturated bond are contained, it will not be limited to these.
Reactive with OH groups in copolymers of OH groups such as 2-hydroxyethyl acrylate, COOH groups such as methacrylic acid and monomers such as acrylic or vinyl compounds copolymerizable therewith A compound obtained by reacting a compound having an epoxy ring with a carbon-carbon unsaturated bond group, for example, a compound such as glycidyl acrylate, can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group and an acryloyl group in addition to the epoxy ring can be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 and JP-A-6-1938, is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali-solubilizing group such as a COOH group and a carbon-carbon unsaturated group include, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH group-containing Polyanethane acrylic oligomer, Diamond Shamrock Co.). Ltd.,) Biscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (Daicel) UCB Co., Ltd.).

Moreover, as the binder resin used in the present embodiment, an alkali-soluble phenol resin can also be used. The alkali-soluble phenol resin can be suitably used when the color composition for color filter of the present embodiment is a positive composition. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A. The above phenols can be used alone or in combination of two or more. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and the like.
Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol, or a mixture thereof and formalin. The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, in the said novolak resin.

Among these various binder resins, the binder resin used in the present embodiment is, from the viewpoint of heat resistance, polyhydroxystyrene resin; polysiloxane resin; (meth) acrylic resin, acrylamide resin, acrylic / acrylamide. Acrylic resins such as copolymer resins are preferred. In addition, acrylic resins such as (meth) acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable from the viewpoint of improving adhesion to a substrate and developing properties described later.
The (meth) acrylic resin includes a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a polymerizable side chain. (Meth) acrylic resins having, for example, Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UC Corporation), dial NR series (Mitsubishi Rayon ( Co., Ltd.), Biscote R264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like are preferable.

The binder resin is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, and the like, and a weight of 2000 to 1 × 10 ⁵ . A coalescence is further preferred, and a polymer of 3000 to 5 × 10 ⁴ is particularly preferred.
Moreover, the usage-amount of binder resin has the preferable range of 10-90 mass% with respect to the total solid in the coloring composition for color filters of this embodiment from viewpoints of developability etc., and 20-80 mass%. The range is more preferable, and the range of 30 to 70% by mass is particularly preferable.

(Crosslinkable monomer)
Any crosslinkable monomer can be used as long as it is photopolymerizable in this embodiment, but it has at least one addition polymerizable ethylene group and has a boiling point of 100 ° C. or higher under normal pressure. Compounds with saturated groups are preferred. Specific examples thereof include monofunctional acrylates and methacrylates such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate And (meth) acrylate obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane; Urethane acrylates as described in JP-B-37193; polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490; epoxy resin And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of (meth) acrylic acid; and mixtures thereof. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

As the crosslinkable monomer, a (meth) acrylic ester monomer is preferable, and a tetrafunctional or higher (meth) acrylic ester monomer is particularly preferable.
The content of the crosslinkable monomer in the composition is preferably from 0.1 to 90% by mass, more preferably from 1.0 to 80% by mass, based on the total solid content, from the viewpoint of curability and the like. The range of 2.0-70 mass% is especially preferable.

(Photopolymerization initiator)
The photopolymerization initiator in the present embodiment is not particularly limited as long as it can polymerize the above-described polymerizable monomer, but may be selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. preferable.
Examples of the photopolymerization initiator include trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, benzoates. Examples include thiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl-substituted coumarin compounds, α-aminoketone compounds, phosphine, and the like. It is preferable to include at least one compound selected from the group consisting of oxide compounds, metallocene compounds, oxime compounds, and triarylimidazole dimers.
The photopolymerization initiator is preferably a compound that does not generate an acid by decomposition.

  Examples of the active halogen compounds such as the halomethyloxadiazole compounds include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Styryl) -1,3,4-oxadiazole and the like.

  As photopolymerization initiators for trihalomethyl-s-triazine compounds, vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho compounds described in JP-A-53-133428) can be used. -1-yl) -4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

  Examples of the α-aminoketone compound include Irgacure series (Irgacure 907, Irgacure 369) manufactured by Ciba Specialty Chemicals, 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2- And methyl-1- [4- (hexyl) phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like.

  The oxime compound is not particularly limited, but 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl)- Butane-1,2-butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid Examples include ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, and the like.

These photopolymerization initiators can be used in combination with a sensitizer and a light stabilizer.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 2-ethyl-9-. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2 -Methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- ( Dimethylamino) phenyl-p-methylstyryl keto Benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, and the like, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, etc. Can be mentioned.

In addition to the above photopolymerization initiators, other known photopolymerization initiators can be used for the color filter coloring composition of the present embodiment.
Specifically, the vicinal polyketol aldonyl compound disclosed in US Pat. No. 2,367,660, US Pat. Nos. 2,367,661 and 2,367,670 are disclosed. Α-carbonyl compounds disclosed in US Pat. No. 2,448,828, acyloin ethers disclosed in US Pat. No. 2,448,828, α-carbonization disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds substituted with hydrogen, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549,367 Triarylimidazole dimer / p-aminophenyl ketone combination disclosed in Japanese Patent No. 51-48516 Compound / trihalomethyl-s-triazine compound and the like.

  The amount of the photopolymerization initiator used is preferably 0.01% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, and more preferably 1% by mass to 20% by mass with respect to the solid content of the crosslinkable monomer. % Range is particularly preferred. When the usage-amount of a photoinitiator exists in the range of 0.01 mass%-50 mass%, it can prevent that molecular weight becomes low too much and film | membrane intensity | strength becomes weak.

(solvent)
The solvent used in the present embodiment is basically not particularly limited as long as the solubility and applicability of the composition are satisfied. Is preferred.
Suitable solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. Of 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate);

2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate Ethyl 2-ethoxy-2-methylpropionate); methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl ether Acetates, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, the solvent used in this embodiment includes methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2- More preferred are heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like.

In the coloring composition for color filter of the present embodiment, various additives, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration as required. An agent or the like can be added.
Specific examples of these additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

  Further, in the case where the alkali solubility in the region to be developed and removed is promoted and the developability is further improved, the colored composition for a color filter of the present embodiment has an organic carboxylic acid, preferably having a molecular weight of 1000 or less. Addition of a low molecular weight organic carboxylic acid can be performed. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<Color filter and liquid crystal display>
The color filter of the present embodiment includes at least a colored layer on a substrate, and the colored layer is formed using the colored composition for a color filter of the present embodiment.
In the color filter of this embodiment, the colored composition for a color filter is applied onto a substrate by a coating method such as spin coating, casting coating, roll coating, and the like to form a colored layer, and exposed through a predetermined mask pattern. And it can manufacture by forming a negative or positive colored pattern by developing with a developing solution. The color filter manufacturing method may include a step of curing the resist pattern by heating and / or exposure, if necessary.
As the radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

Examples of the substrate include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements, and those obtained by attaching a transparent conductive film to these, and photoelectric conversion element substrates used for imaging elements, for example, A silicon substrate, a complementary metal oxide semiconductor (CMOS), etc. are mentioned. These substrates may be formed with black stripes that optically isolate each pixel.
If necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.

As the developer used in the production of the color filter of the present embodiment, any developer can be used as long as it dissolves the color filter coloring composition of the present embodiment and does not dissolve the radiation irradiated portion. . Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
As said organic solvent, the above-mentioned solvent used when preparing the composition of this embodiment is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Concentration of an alkaline compound such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution dissolved in this manner is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

The color filter of the present embodiment can be used for a solid-state imaging device such as an organic or inorganic EL element, a liquid crystal display element, or a CCD, and the display device of the present embodiment includes this color filter.
For example, as shown in FIG. 1, the liquid crystal display device 40 of the present invention has the obtained color filter 10 (display side substrate) and a counter substrate 20 having a TFT array substrate (liquid crystal drive side substrate) facing each other. When the inner peripheral edge of the substrate is bonded with a sealant, the two substrates are bonded together while maintaining a cell gap of a predetermined distance. An active matrix color liquid crystal display device belonging to a liquid crystal panel can be obtained by filling the liquid crystal layer 30 with a liquid crystal layer 30 and sealing the gap between the substrates. Here, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.
In the case of an organic EL element, for example, the color filter of the present invention can be laminated on the light emitting layer.

(Protective layer)
In the color filter of the present embodiment, a transparent resin layer can be formed so as to cover the colored layer for the purpose of protecting the color filter (hereinafter referred to as “protective layer”). The said protective layer can use a well-known negative type photocurable transparent resin composition or a thermosetting transparent resin composition, and is selected from the group which consists of an acrylic resin, a methacryl resin, a polyimide resin, and an epoxy resin. It is preferable from the point of transparency and intensity | strength to be formed from at least 1 type of resin.
By providing such a protective layer, the problems of NMP resistance and electrical reliability can be overcome. However, since the protective layer is generally made of a photocurable or thermosetting organic resin, the solution is applied to a colored coating film. Solvent resistance with respect to the solvent used at the time of application | coating is required.
On the other hand, the coloring composition for a color filter of the present invention is excellent in NMP resistance without providing a protective layer, and is used when forming a protective layer even when a protective layer is provided. It is suitable as a coloring composition for a color filter because it has resistance to a solvent.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1
(Synthesis of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt)
5 g (24.3 mmol) of p-vinylbenzenesulfonic acid sodium salt and 1 mL of N, N-dimethylformamide (DMF) were added to 50 mL of n-heptane, and 4.51 g (37.9 mmol) of thionyl chloride was added dropwise at room temperature. After completion of the dropwise addition, the internal temperature was controlled at 70 to 75 ° C. and reacted for 2 hours. The n-heptane layer was separated, and the organic layer was washed with 5% aqueous sodium hydrogen carbonate solution and then with water. The organic layer was dehydrated with sodium sulfate and concentrated to obtain p-vinylbenzenesulfonyl chloride. The yield was 1.83 g (yield: 37%).
Next, 1.34 g (9.00 mmol) of trifluoromethanesulfonamide manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 25 mL of methylene chloride, and the internal temperature was cooled to 5 ° C. or lower. 1.82 g (18.0 mmol) of triethylamine manufactured by Wako Pure Chemical Industries, Ltd. was added dropwise so that the internal temperature did not exceed 10 ° C., and 1.83 g of p-vinylbenzenesulfonyl chloride synthesized at 10 ° C. or less after completion of the addition ( 9.0 mmol) was added. After stirring at 5 ° C. or lower for 1 hour, the mixture was further stirred at room temperature for 5 hours, and 100 mL of water was added to the reaction solution for extraction. The separated organic layer was washed with water, dehydrated with sodium sulfate, and the organic layer was concentrated under reduced pressure with an evaporator. 2.98 g of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt represented by the following structural formula (5) (Yield 79%) was obtained.
About the said (p-vinylphenyl) trifluoromethanesulfonyl imido acid triethylamine salt (Structural formula 13), it confirmed that it was the target compound from the following analysis result.
MS (ESI) (m / z): 102 (+), 314 (-)
Elemental analysis value: CHN actual measurement value (42.93%, 5.42%, 6.94%); theoretical value (43.26%, 5.57%, 6.73%)

(Synthesis of dyes)
1.85 g (3.60 mmol) of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. represented by the following structural formula (4) was dissolved in 30 mL of methanol, and the following structural formula (5 ) 1.50 g (3.60 mmol) was added while stirring the (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt represented by (), and the mixture was further stirred at room temperature for 1 hour. Methanol in the solution was concentrated with an evaporator, 100 mL of water was added, and the precipitate was collected by filtration and washed with water. The cake was dried under reduced pressure to obtain 2.33 g (yield 82%) of dye A represented by the exemplified compound (1). About dye A represented by exemplary compound (1), it confirmed that it was the target compound from the following analysis result.
MS (ESI) (m / z): 478 (+), 314 (-)
Elemental analysis values: CHN actual measurement values (63.78%, 6.09%, 7.11%); theoretical values (63.62%, 5.97%, 7.07%)

(Preparation of coloring composition for color filter)
First, a photosensitive transparent resin composition having the following composition was prepared.
PGMEA solution of acrylic acid resin (active ingredient 42% by mass, resin (benzyl methacrylate / methacrylic acid = 62/38 (mass ratio)), acid value: 70 mgKOH / g, weight average molecular weight: 9000, PGMEA = propylene glycol monomethyl ether Acetate): 18 parts by mass. Multifunctional acrylate monomer (SR399E, Sakai Chemical): 8 parts by mass. Photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1- On (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals): 2 parts by mass / photosensitizer (4,4′-dimethylaminobenzophenone): 0.2 parts by mass

(Preparation of coloring composition M for color filter)
The following components were mixed and stirred to prepare a colored resin composition M having a non-volatile component of 30% by mass.
-PGMEA solution of 10% by weight of dye A: 10 parts by mass-Photosensitive transparent resin composition: 20 parts by mass-Fluorine-based additive (Megafac R-08MH (manufactured by DIC Corporation)): 0.02 parts by mass・ PGMEA: 2 parts by mass

(Preparation of coloring composition N for color filter)
The following components were mixed and stirred to prepare a colored resin composition N (mixed system of dye and pigment) having a non-volatile component of 30% by mass.
・ 10 mass% PGMEA solution of dye A: 2 mass parts ・ 50 mass% dispersed pigment liquid: 12 mass parts ・ Photosensitive transparent resin composition: 20 mass parts ・ Fluorine-based additive (Megafac R-08MH (DIC ( Co., Ltd.)): 0.02 parts by mass / PGMEA: 2 parts by mass The above-mentioned dispersed pigment liquid is C.I. I. Pigment Blue 15: 6 / C.I. I. Pigment Bio Red 23 = 85/15 (by weight) mixture, 12 parts by mass, Dispersbyk-2001 (produced by Big Chemie) as a dispersant, 18 parts by mass (in terms of solid content), and 60 parts by mass of propylene glycol monomethyl ether acetate as a solvent Was prepared by treating with a bead mill.

(Preparation of protective layer forming material)
The following components were mixed and stirred to prepare a protective layer forming material solution having a non-volatile component of 20% by mass.
As a monomer, 45 parts by mass of dipentaerythritol pentaacrylate (DPPA) As a photopolymerization initiator, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)) 2 parts by mass as binder resin, methacrylic acid / methyl methacrylate copolymer (weight average molecular weight: 10,000, mass ratio of methacrylic acid / methyl methacrylate 70/30) 23 parts by mass as solvent 280 parts by mass of cyclohexanol acetate

(Evaluation 1: Evaluation of NMP resistance, heat resistance and light resistance)
Using the above colored resin compositions M and N as a coating liquid, this was applied onto a glass substrate by a spin coating method, dried at 80 ° C., and exposed to ultraviolet light from the coating film side with a high-pressure mercury lamp at 100 mJ / m ² , A coating film for evaluation was prepared by curing. Using this coating film, NMP resistance, CHXA resistance, and heat resistance were evaluated by the following methods.

-NMP resistance-
As a sample for NMP resistance evaluation, NMP resistance was evaluated using a coating film which was cured by exposure at 230 ° C. for 30 minutes after exposure and curing with a high-pressure mercury lamp (in the table, described as having no protective layer). . Further, the above-mentioned protective layer forming material solution is applied onto the cured coating film by the spin coating method in the same manner as described above, and exposure and curing are performed under the same conditions as described above, and heat curing at 230 ° C. for 30 minutes. Thus, a protective layer was formed. Using this protective layer, NMP resistance was evaluated (in the table, described as having a protective layer).
For NMP resistance, one drop of NMP is applied to the surface of the coating film on the glass substrate, and after standing for 10 seconds, the NMP is wiped with a wipe (Bencott Lint Free AZ-8, manufactured by Gardner). The coating film spectrum before and after the NMP dropping, that is, the ΔEab value was measured by using a microspectroscope OSP-SP200 manufactured by Olympus Co., Ltd. and evaluated by calculating a color difference. It can be said that the smaller the color difference, the less elution by NMP and the higher the resistance to NMP.

-CHXA resistance-
The solvent used was changed from NMP to CHXA (cyclohexanol acetate), and CHXA resistance was evaluated by the same procedure as the above NMP resistance evaluation.

-Heat resistance-
The glass substrate on which the coating film was prepared was placed on a hot plate so that the substrate surface was in contact, left at 80 ° C. for 3 minutes, and then exposed to 200 mJ / m ² with a high-pressure mercury lamp. Next, the glass substrate was processed under the following conditions (a) or (b). The color difference (ΔEab value) before and after the treatment was calculated in the same manner as described above. A smaller ΔEab value indicates better heat resistance.
Condition (a): left at 200 ° C. for 30 minutes.
Condition (b): left at 230 ° C. for 30 minutes.

(Evaluation 2: Evaluation of electrical reliability)
−Measurement of voltage holding ratio−
As a layer structure, a measurement cell comprising a glass substrate / ITO (indium tin oxide) electrode / coating film comprising the above colored resin composition / liquid crystal / ITO electrode was prepared, and a voltage holding ratio measurement system (VHR-) was prepared under the following conditions. The voltage holding ratio was measured using 1A type (manufactured by Toyo Technica Co., Ltd.) (described as “no protective layer” in the table). In addition, a measurement cell comprising a glass substrate / ITO (indium tin oxide) electrode / coating film / protective layer / liquid crystal / ITO electrode comprising the above colored resin composition was prepared, and the voltage holding ratio was measured in the same manner as described above. (Described as having a protective layer in the table).
(conditions)
Distance between ITO electrodes: 5 μm
Applied voltage pulse amplitude: 5V
Applied voltage pulse frequency: 60 Hz
Applied voltage pulse width: 16.67 msec
In addition, the coating film which consists of the said colored resin composition was specifically produced with the following method.
(Preparation method of coating film)
The colored resin composition was applied to the ITO electrode side of the glass substrate with a spin coater and prebaked to form a coating film having a thickness of 2.0 to 2.4 μm. Subsequently, the coating film was irradiated with ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm in a predetermined pattern with an exposure amount of 60 mJ / cm ² . Then, it developed using 0.04 mass% potassium hydroxide aqueous solution, wash | cleaned with pure water for 1 minute, dried, the substrate was post-baked, and the coating film which consists of the said colored resin composition was produced.
In this evaluation, it can be evaluated that the electrical reliability is high when the voltage holding ratio is 80% or more.

Example 2
In Example 1, instead of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, 1.70 g of (p-acryloyloxyphenyl) trifluoromethanesulfonylimidic acid triethylamine salt represented by the following structural formula (6) ( Except that 3.69 mmol) was used, in the same manner as in Example 1, 2.67 g (yield 86%) of dye B represented by the exemplified compound (2) was obtained. About dye B represented by exemplary compound (2), it confirmed that it was the target compound from the following analysis result.
MS (ESI) (m / z): 478 (+), 358 (-)
Elemental analysis values: CHN measured values (61.95%, 5.43%, 6.41%); theoretical values (61.71%, 5.66%, 6.69%)

Example 3
In Example 1, instead of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt, 2.00 g of (p-acryloyloxybutoxyphenyl) trifluoromethanesulfonylimidic acid triethylamine salt represented by the following structural formula (7) ( 2.63 mmol) was used in the same manner as in Example 1 to obtain 2.15 g (yield 78%) of the dye C represented by the exemplified compound (3). It was confirmed that the dye C represented by the exemplified compound (3) was the target compound from the following analysis results.
MS (ESI) (m / z): 478 (+), 430 (-)
Elemental analysis values: CHN measured values (62.32%, 6.38%, 6.22%); theoretical values (62.10%, 6.10%, 6.16%)

Comparative Example 1
In Example 1, evaluation was performed in the same manner as in Example 1 except that the compound represented by the following structural formula (8) was used instead of the dye A. In addition, in the synthesis | combination of the dye in Example 1, the compound shown by following Structural formula (8) used the Aldrich bistrifluoromethanesulfonylimide for equimolarity instead of (p-vinylphenyl) trifluoromethanesulfonyl imido acid triethylamine salt. Except for the above, it was synthesized in the same manner as in Example 1 to obtain 7.31 g in a yield of 99%.

As shown in the results of Table 1, the triarylmethane dyes of Examples 1 to 3 using a sulfonylimido acid ion having a photocuring group introduced as a counter anion have good heat resistance, and NMP or protection It turns out that the tolerance with respect to CHXA which is a solvent used for a layer, and a voltage holding ratio are high.
On the other hand, in a comparative example using a triarylmethane dye that does not have a photocuring group different from the present invention, the heat resistance is good, but the resistance to CHXA, which is a solvent used in NMP and a protective layer, is insufficient. In particular, since the voltage holding ratio is inferior, it is difficult to use for color filters used in liquid crystal displays.
Moreover, when the dye of the present invention is mixed with a dispersed pigment and evaluated in the same manner, the effect of the photocuring group appears more remarkably.

When a colored layer is formed using the coloring composition for a color filter of the present invention, it is not only electrochemically and thermally stable, but also has good solubility in organic solvents and resins, and development solubility is improved. A color filter with excellent resistance to NMP and high electrical reliability can be obtained.
For this reason, the color filter of this invention is suitable for color filters, such as an organic or inorganic EL element, a liquid crystal display element, and CCD.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device

Claims (9)

A coloring composition for a color filter comprising a binder resin, a crosslinkable monomer, a photopolymerization initiator, a colorant and a solvent, wherein the colorant is a triarylmethane dye represented by the following general formula (I).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Any one of aryl groups, and any of R ¹ and R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to form part of a ring structure or heterocyclic structure; X in the formula is an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, Y represents a divalent hydrocarbon group, and Z is a photoreactive group.)   The coloring composition for a color filter according to claim 1, wherein Y in the general formula (I) is an arylene group.   The colored composition for a color filter according to claim 1 or 2, wherein Z in the general formula (I) is a group selected from a vinyl group, an allyl group, a (meth) acryl group, and a (meth) acryloyl group.   The coloring composition for a color filter according to any one of claims 1 to 3, wherein X in the general formula (I) is a perfluoroalkyl group. R ⁵ in the general formula (I) is a hydrogen atom, and R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms. The coloring composition for color filters of any one of Claims 1. The coloring composition for a color filter according to claim 5, wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are all the same.   Furthermore, the coloring composition for color filters of any one of Claims 1-6 containing a pigment.   A color filter comprising at least a colored layer on a substrate, wherein the colored layer is formed using the colored composition for a color filter according to any one of claims 1 to 7.   A liquid crystal display device comprising: the color filter according to claim 8; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.

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