JP2012194466A - Colored composition for color filter and color filter using the same, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter that is excellent in development solubility and has high resistance to NMP and high electric reliability.SOLUTION: A colored composition for a color filter contains a binder resin, a cross-linkable monomer, a photopolymerization initiator, a colorant and a solvent. The colorant contains a cationic dye represented by general formula (I) and a polymer derived from an anionic compound and an epoxy compound.

Description

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

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.
Triarylmethane dyes are known as materials used in the colored layer, and examples of using aromatic sulfonic acid as a counter anion of triarylmethane dyes are known to improve durability to heat and light. (For example, refer to 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).
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.
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.

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. Further, since the number of steps increases for forming the protective layer, it is not desirable to use the protective layer.

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 diligent study to solve the above-mentioned problems, the present inventor introduced a cationic dye in a triarylmethane dye as a colorant for a color filter coloring composition and an ethylenically unsaturated bond as a counter anion. By using the specific sulfonylimide acid ion and copolymerizing the counter anion and an epoxy compound having an ethylenically unsaturated bond, the solubility and light resistance to organic solvents and resins are maintained while maintaining heat resistance. It was found that the resistance to NMP can be improved, and further high electrical reliability can be obtained. In addition, the present inventor has obtained a coating film by copolymerizing the counter anion, an epoxy compound having an ethylenically unsaturated bond, and a compound having an ethylenically unsaturated bond such as a macromonomer in the colorant. As a result, the present inventors have found that the contrast and heat resistance can be improved.

That is, the present invention
(1) A binder resin, a crosslinkable monomer, a photopolymerization initiator, a colorant and a solvent, wherein the colorant is (A) a cationic dye represented by the following general formula (I), and (B) the following general A coloring composition for a color filter comprising a polymer comprising a structural unit derived from an anionic compound represented by formula (II) and a structural unit derived from a compound represented by the following general formula (III):

Wherein (I), R ¹ ~R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group, or an aryl group which may have a substituent, R ¹ And R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to each other to form a part of a ring structure or a heterocyclic structure. ]

[In formula (II), R ⁷ represents a hydrogen atom or a methyl group. X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, and Y represents a divalent organic group. ]

[In formula (III), R ⁸ represents a hydrogen atom or a methyl group. A represents a divalent organic group. ]

(2) The component (B) is a structural unit derived from the anionic compound represented by the general formula (II), a structural unit derived from the compound represented by the general formula (III), and an ethylenic compound. The coloring composition for a color filter according to the above (1), which is a polymer composed of a structural unit derived from a compound containing a functional group having a saturated bond,
(3) The colored composition for a color filter according to (2), wherein at least one of the compounds containing a functional group having an ethylenically unsaturated bond is a macromonomer,
(4) The coloring composition for a color filter according to (3), wherein the macromonomer includes a structural unit represented by the following general formula (IV) and / or (V):

[In formula (IV), R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ¹¹ ) —CH (R ¹² ) —O] _a —R ¹³ , — [(CH ₂ ) _b —O] _c —R ¹³ , — [CO— (CH ₂ ) _b —O] _c —R ¹³ , —CO—O—R ¹⁴ or a monovalent group represented by —O—CO—R ¹⁵ .
R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group.
R ¹³ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹⁶ , and R ¹⁶ is a hydrogen atom An atom or an alkyl group having 1 to 5 carbon atoms is shown.
R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ¹¹ ) —CH (R ¹² ) —O] _a —R ¹³ , — [(CH ₂ ) _b A monovalent group represented by —O] _c —R ¹³ or — [CO— (CH ₂ ) _b —O] _c —R ¹³ ;
R ¹⁵ represents an alkyl group having 1 to 18 carbon atoms.
The alkyl group, aralkyl group, or aryl group contained in R ¹⁰ may have a substituent.
k represents an integer of 5 to 200. a represents an integer of 1 to 18, b represents an integer of 1 to 5, and c represents an integer of 1 to 18. ]

[In the formula (V), m represents an integer of 1 to 5, and n represents an integer of 5 to 200. ]

(5) The macromonomer has a structure in which a functional group having an ethylenically unsaturated bond and a structural unit represented by the general formula (IV) or (V) are linked via a divalent organic group. A coloring composition for a color filter according to the above (4),
(6) The colored composition for a color filter according to any one of (2) to (5), wherein the functional group having an ethylenically unsaturated bond is a (meth) acryloyl group, a vinyl group, or an allyl group. ,
(7) The colored composition for a color filter according to any one of (1) to (6), wherein X in the general formula (II) is a perfluoroalkyl group,
(8) 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 an alkyl group having 1 to 20 carbon atoms. (7) The coloring composition for color filters in any one of
(9) The coloring composition for a color filter according to any one of (1) to (8), further including a pigment,
(10) 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 (1) to (9), and ,
(11) A liquid crystal display device comprising the color filter according to (10), 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, as well as excellent resistance to NMP and excellent electrical reliability. A colored composition for a filter, 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 color composition for color filter of this embodiment contains a binder resin, a crosslinkable monomer, a photopolymerization initiator, a colorant and a solvent, and the colorant is (A) a cation represented by the following general formula (I). And (B) a polymer containing a structural unit derived from an anionic compound represented by the following general formula (II) and a structural unit derived from a compound represented by the following general formula (III) It is characterized by doing.

In the above formula (I), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹ And R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to each other to form a part of a ring structure or a heterocyclic structure.

In the above formula (II), R ⁷ represents a hydrogen atom or a methyl group. X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, and Y represents a divalent organic group.

In said formula (III), R < ⁸ > shows a hydrogen atom or a methyl group. A represents a divalent organic group.

(Coloring agent)
First, the colorant in the present embodiment will be described.
The colorant in the present embodiment includes (A) a cationic dye represented by the general formula (I), and (B) a structural unit derived from the anionic compound represented by the general formula (II), and the general formula ( And a polymer containing a structural unit derived from the compound represented by III).

[(A) Cationic dye]
The (A) cationic dye in this embodiment is represented by the following general formula (I).

In the above formula (I), R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ¹ And R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to each other to form a part of a ring structure or a heterocyclic structure.

In the general formula (I), examples of the alkyl group in R ^{1 to} R ⁶ include a saturated alkyl group, an unsaturated alkyl group, and a cycloalkyl group, and these include an aryl group, an alkyloxy group, an aryloxy group, It may have a substituent such as an acyloxy group, a halogen atom, an acylamino group, an alkyloxycarbonyl group, an aminocarbonyl group, a hydroxy group and a cyano group.
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 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. The alkyl group is preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably an ethyl group or 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.

  Examples of the cationic dye represented by the general formula (I) include compounds represented by the following exemplary compound (1).

  The cationic dye represented by (A) 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.

[(B) polymer]
The colorant in the present embodiment is represented by (B) a cationic dye, (B) a structural unit derived from an anionic compound represented by the following general formula (II), and the following general formula (III). And a polymer containing a structural unit derived from the compound.
That is, the polymer is a polymer obtained by copolymerizing at least the anionic compound represented by the general formula (II) and the compound represented by the general formula (III).

In the above formula (II), R ⁷ represents a hydrogen atom or a methyl group. X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, and Y represents a divalent organic group.

In said formula (III), R < ⁸ > shows a hydrogen atom or a methyl group. A represents a divalent organic group.

The anionic compound represented by the general formula (II) is a sulfonylimide acid ion having an ethylenically unsaturated bond, and is a counter anion of the (A) cationic dye.
In the general formula (II), 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 hydrogen atoms may be substituted with fluorine atoms. In particular, a fluorinated alkyl group having 1 to 3 carbon atoms, in which some or all of the hydrogen atoms are substituted with fluorine atoms, and among them, a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms, This is particularly preferable in terms of increasing the acidity of the imide 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, the divalent organic group represented by Y is not particularly limited, and for example, a linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 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.

  Examples of the anionic compound represented by the general formula (II) include the following exemplary compounds (2) to (4).

  These anionic compounds may be used alone or in combination of two or more.

Next, the compound represented by the general formula (III) is an epoxy compound having an ethylenically unsaturated bond, and in the general formula (III), R ⁸ represents a hydrogen atom or a methyl group.
In the general formula (III), the divalent organic group represented by A is not particularly limited. Or a branched oxyalkylene group, a carbonyloxyalkylene group, etc. are mentioned. Specifically, the alkylene group includes a methylene group, ethylene group, n-propylene group, isopropylene group, various butylene groups, and the oxyalkylene group includes ethylene oxide, propylene oxide, butylene oxide, and the like. Examples of the carbonyloxyalkylene group include a carbonyloxymethylene group. Among these, a carbonyloxyalkylene group is preferable from the viewpoint of availability of raw materials and production, and a carbonyloxymethylene group is particularly preferable.

Examples of the compound represented by the general formula (III) include glycidyl (meth) acrylate.
These compounds may be used alone or in combination of two or more.

In the present embodiment, the structural unit (B) is derived from the compound represented by the general formula (III) in addition to the structural unit derived from the anionic compound represented by the general formula (II). By including, the color filter using the coloring composition containing the colorant has NMP resistance and high electrical reliability.
The reason for this is that when the coating film of the coloring composition containing the colorant is heated, the epoxy group contained as a component of the coloring agent is added to the acrylic resin contained in the coloring composition as a binder resin. It is considered that the colorant is immobilized in the coating film because it can cause a thermosetting reaction with the carboxylic acid group contained, and as a result, the colorant is hardly eluted from the coating film. In addition, since the reaction in the coating film occurs without a solvent, not all epoxy groups contained in the colorant are uniform and do not complete the reaction without excess or deficiency. Since the colorant contains a plurality of epoxy groups in the same molecule, if any one of the epoxy groups reacts with a component in the coating film, it is fixed in the coating film, and has the desired high NMP resistance and electrical reliability. It becomes possible to have sex.

The polymer (B) includes the structural unit derived from the anionic compound represented by the general formula (II) and the structural unit derived from the compound represented by the general formula (III). A constitutional unit derived from a compound containing a functional group having an ethylenically unsaturated bond other than the compounds represented by II) and (III) may be included.
By including the structural unit, it contributes to improved compatibility with components other than the colorant contained in the coloring composition, and as a result, phase separation caused by the colorant component can be suppressed. Compared with a polymer composed only of a structural unit derived from the anionic compound represented by the general formula (II) and a structural unit derived from the compound represented by the general formula (III), the color filter obtained Contrast and heat resistance can be improved.

The functional group having an ethylenically unsaturated bond is preferably a functional group having an ethylenic double bond, specifically, a vinyl group, an allyl group, a (meth) acryl group, or a (meth) acryloyl group. And vinyl cycloalkyl group. Among these, a vinyl group, an allyl group, a (meth) acryl group, and a (meth) acryloyl group are preferable from the viewpoints of reactivity and ease of synthesis.
The compound containing a functional group having an ethylenically unsaturated bond is preferably a compound containing a functional group having one ethylenically unsaturated bond in the molecule from the viewpoint of ease of production.

As a compound containing the functional group which has the said ethylenically unsaturated bond, a C1-C10 alkyl (meth) acrylate, the macromonomer mentioned later, etc. are mentioned, for example.
These compounds may be used alone or in combination of two or more.

In the present embodiment, the compound containing a functional group having an ethylenically unsaturated bond is preferably a macromonomer from the viewpoint of improving the contrast of a color filter using the colored composition of the present embodiment, and heat resistance. . The macromonomer in the present embodiment refers to a compound having a weight average molecular weight of 1000 or more and containing a functional group having preferably one ethylenically unsaturated bond in the molecule.
From the viewpoint of ensuring the concentration of the cationic dye component contained in the colorant in the coloring composition, the weight average molecular weight of the macromonomer is preferably in the range of 1000 to 10,000.

  Although there is no restriction | limiting in particular about the structure of the said macromonomer, For example, the macromonomer containing the structural unit represented by the following general formula (IV) and / or (V) is used preferably.

In said formula (IV), R < ⁹ > shows a hydrogen atom or a methyl group, R < ¹⁰ > is a C1-C18 alkyl group, an aralkyl group, an aryl group, a cyano group,-[CH (R < ¹¹ >)-CH. (R ¹² ) —O] _a —R ¹³ , — [(CH ₂ ) _b —O] _c —R ¹³ , — [CO— (CH ₂ ) _b —O] _c —R ¹³ , —CO—O—R ¹⁴ or a monovalent group represented by —O—CO—R ¹⁵ .
R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group.
R ¹³ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹⁶ , and R ¹⁶ is a hydrogen atom An atom or an alkyl group having 1 to 5 carbon atoms is shown.
R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ¹¹ ) —CH (R ¹² ) —O] _a —R ¹³ , — [(CH ₂ ) _b A monovalent group represented by —O] _c —R ¹³ or — [CO— (CH ₂ ) _b —O] _c —R ¹³ ;
R ¹⁵ represents an alkyl group having 1 to 18 carbon atoms.
The alkyl group, aralkyl group, or aryl group contained in R ¹⁰ may have a substituent.
k represents an integer of 5 to 200, and is preferably an integer of 5 to 30 from the viewpoint of ensuring compatibility in the colored composition coating film and the concentration of the cationic dye component contained in the colorant. a represents an integer of 1 to 18, b represents an integer of 1 to 5, and c represents an integer of 1 to 18.

  In the above formula (V), m represents an integer of 1 to 5, n represents an integer of 5 to 200, and ensures compatibility with the colored composition coating film and the concentration of the cationic dye component contained in the colorant. Therefore, n is preferably an integer of 5 to 30.

Among the structural units represented by the general formula (IV) and / or (V), in the general formula (IV), R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is —CO—O—R ¹⁴ . R ¹⁴ is an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ¹¹ ) —CH (R ¹² ) —O] _a —R ¹³ , — [(CH ₂ ) _b -O] _c -R ^13, or _{- [CO- (CH 2) b} -O] and more preferably a macromonomer containing monovalent structural unit is a group represented by _c -R ^13. R ^{11 to} R ¹³ and a to c are the same as described above.
As such a structural unit, for example, an alkyl (meth) acrylate having 1 to 18 carbon atoms, benzyl (meth) acrylate, acrylonitrile, a polyalkylene glycol mono (meth) acrylate having 1 to 5 carbon atoms, a caprolactone-modified mono (meta) ) And other structural units derived from acrylates. Among these, the structural unit derived from a C1-C18 alkyl (meth) acrylate is preferable.
The macromonomer may contain only one type of the structural unit or may contain two or more types.

From the viewpoint of production of the macromonomer, the macromonomer is a divalent organic group in which the functional group having the ethylenically unsaturated bond and the structural unit represented by the general formula (IV) or (V) are divalent. It is more preferable that the structure has a structure connected via the.
The divalent organic group is not particularly limited, but from the viewpoint of production of a macromonomer, the functional group having the ethylenically unsaturated bond and the structure represented by the general formula (IV) or (V) An organic group containing a structure derived from a reactive functional group for linking units is preferable. Examples of the reactive functional group include a hydroxyl group, an isocyanate group, a thiol group, an amino group, an aldehyde group, and a carboxyl group.
The production method of the macromonomer is not particularly limited, and for example, a living polymerization method and a radical polymerization method using a chain transfer agent are well known. The radical polymerization method is easier to use because it has a greater degree of freedom in monomer selection. For example, an oligomer having a carboxyl group at one end can be obtained by radical polymerization of a monomer in the presence of a chain transfer agent having a carboxyl group such as mercaptopropionic acid. When glycidyl methacrylate is added to this oligomer, an oligomer having a methacryloyl group at one end, that is, a macromonomer in this embodiment is obtained.
Such a macromonomer may be appropriately synthesized or may be a commercially available product. Commercially available macromonomers include, for example, one-end methacryloylated poly-n-butyl acrylate oligomer (weight average molecular weight: 6000, “AB-6 (trade name)” manufactured by Toagosei Chemical Co., Ltd.), caprolactone-modified hydroxyethyl. Methacrylate (“Placcel FM5 (trade name)” manufactured by Daicel Chemical Industries, Ltd.), caprolactone-modified hydroxyethyl acrylate (“Placcel FA10L (trade name)” manufactured by Daicel Chemical Industries, Ltd.) and the like can be mentioned.
Other commercially available macromonomers that may be included include, for example, one-end methacryloylated polymethylmethacrylate oligomer (weight average molecular weight: 6000, “AA-6 (trade name)” manufactured by Toagosei Chemical Co., Ltd.), One-end methacryloylated polystyrene oligomer (weight average molecular weight: 6000, “AS-6 (trade name)” manufactured by Toagosei Co., Ltd.) and the like.

A structural unit derived from an anionic compound represented by the general formula (II) and a structural unit derived from a compound represented by the following general formula (III), preferably a functional group further having an ethylenically unsaturated bond The molecular weight of the polymer (B) in the present embodiment, which is composed of structural units derived from a compound containing, ensures compatibility with the colored composition coating film and the concentration of the cationic dye component contained in the colorant. From the viewpoint, the weight average molecular weight (Mw) is preferably 2000 to 20000, and the number average molecular weight (Mn) is preferably 2000 to 10,000. Moreover, it is preferable that molecular weight distribution (Mw / Mn) is 1.0-4.0.
The polymer (B) in the present embodiment contains an ion pair of the cationic dye (A) and the anionic compound represented by the general formula (II), so that its molecular weight is directly determined by gel permeation. Although it is difficult to measure using an Aation Chromatography (GPC) method, styrene (manufactured by Kanto Chemical Co., Inc.) instead of the anionic compound represented by the general formula (II) as a model polymer of the colored composition ) And the like, the molecular weight of the polymer produced under the same reaction conditions is measured using the GPC method, and the approximate molecular weight of the colorant can be estimated.

Here, since the anionic compound represented by the general formula (II) is also a counter anion of the (A) cationic dye, in the colorant in the present embodiment, the (A) cationic dye, The structural unit derived from the anionic compound represented by the general formula (II) is an equimolar amount. Therefore, in the polymer (B), the lower the proportion of the structural unit derived from the compound other than the anionic compound relative to the structural unit derived from the anionic compound represented by the general formula (II), It is preferable at the point that the density | concentration of (A) cationic dye in an agent becomes high. On the other hand, if the proportion of the structural unit derived from the compound other than the anionic compound in the polymer (B) is too low, the color filter containing the colorant contributes to NMP resistance and electrical reliability. Lower.
From the above viewpoint, in the polymer (B), the mass ratio of the structural unit derived from the anionic compound represented by the general formula (II) and other structural units is 1 / 0.5 to 1 / 20 is preferable, and 1/1 to 1/10 is more preferable.

When the polymer (B) is composed of a structural unit derived from the anionic compound represented by the general formula (II) and a structural unit derived from the compound represented by the general formula (III) The mass ratio of the structural units is preferably 1 / 0.5 to 1/10 from the viewpoints of NMP resistance, electrical reliability, contrast, and heat resistance of the color filter containing the colorant. 1/1 to 1/6 is more preferable, and 1/1 to 1/3 is still more preferable.
When the ratio of the structural unit derived from the compound represented by the general formula (III) in the polymer (B) is too high, other than the colorant containing the polymer and the colorant contained in the color composition It is thought that it is easy to induce phase separation with the components of the above, but by setting the mass ratio of the structural units derived from the compounds represented by the general formulas (II) and (III) to the above range, a colored composition Since the compatibility of each component contained in the product can be ensured and phase separation can be suppressed, the characteristics of the color filter can be improved.

  Further, the polymer (B) is a structural unit derived from the anionic compound represented by the general formula (II), a structural unit derived from the compound represented by the general formula (III), and an ethylenic group. When comprising a structural unit derived from a compound containing a functional group having a saturated bond, the structural unit derived from the compound represented by the general formula (III) in the polymer (B), and ethylenically unsaturated The mass ratio with respect to the structural unit derived from the compound containing a functional group having a bond is 1 / 0.0. From the viewpoints of NMP resistance, electrical reliability, contrast, and heat resistance of the color filter containing the colorant. 5 to 1/20 is preferable, 1/1 to 1/10 is more preferable, and 1/1 to 1/5 is still more preferable.

The method for producing the polymer (B) includes an anionic compound represented by the general formula (II), a compound represented by the general formula (III), and preferably a functional group having an ethylenically unsaturated bond. Any method can be used without particular limitation as long as it can copolymerize a compound containing. For example, a reaction of a salt of the compound represented by the general formula (II), a compound represented by the general formula (III), and a compound further preferably containing a functional group having an ethylenically unsaturated bond. A method of producing by thermal radical polymerization in a solvent is preferred.
The reaction solvent is not particularly limited as long as it can dissolve the above compound and its polymer. Examples thereof include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[Production method of colorant]
In the present embodiment, the colorant containing the (A) cationic dye and the (B) polymer is, for example, a counter anion in the solution of the (B) polymer obtained as described above. Cl ^- (a) is a cationic dye represented by addition, it can be synthesized by a salt exchange.
Specifically, the dissolved (B) polymer in the reaction solvent, counter anion Cl ^- (A) is a cationic dye represented by addition, after stirring, combining the resulting precipitate by removing by filtration it can. (A) Cationic dye is added so that it may become equimolar amount with respect to the structural unit derived from the anionic compound represented by the said general formula (II) in (B) polymer. Examples of the reaction solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and methanol, ethanol, isopropyl alcohol, n-butyl alcohol, 2-ethoxyethanol, and 1-methoxy-2-propanol. Alcohols or a mixed solvent thereof may be mentioned, and the reaction temperature is preferably 0 ° C. to 40 ° C., for example.

  The colorant may contain an organic pigment in addition to (A) the cationic dye represented by the general formula (I). 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. These pigment dispersants 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. A compound having a saturated group is 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), 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl manufactured by BASF Corporation. Examples include -1- [4- (hexyl) phenyl] -2-morpholinopropan-1-one and 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

  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, but the colored composition for color filter of the present invention is excellent in NMP resistance and electrical reliability without providing a protective layer. Therefore, it is suitable as a coloring composition for a color filter. Moreover, even if a protective layer is provided, the performance suitable as a coloring composition for a color filter using the coloring agent does not deteriorate.

  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.

[Synthesis 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. 1.2 g (18.0 mmol) of triethylamine manufactured by Wako Pure Chemical Industries, Ltd. was dropped so that the internal temperature did not exceed 10 ° C., and the synthesized p-vinylbenzenesulfonyl chloride 1. 83 g (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 is washed with water, dehydrated with sodium sulfate, and the organic layer is concentrated under reduced pressure using an evaporator. 2.95 g of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt represented by the following structural formula (5) (Yield 90%) was obtained.
About the said (p-vinylphenyl) trifluoromethanesulfonyl imido acid triethylamine salt, 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 Example 2]
(Synthesis of polymer 1)
10 g of cyclohexanone was added to a reaction vessel equipped with a condenser, and 2.73 g (7.5 mmol) of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt obtained in Synthesis Example 1 and glycidyl methacrylate manufactured by Kanto Chemical Co., Inc. (Product name: glycidyl methacrylate) 3.2 g (22.5 mmol) was dissolved. To this was added 47 mg (0.6 mmol) of 2-mercaptoethanol, and the mixture was heated to 100 ° C. and stirred. While stirring, a solution of 49 mg (0.3 mmol) of α, α′-azobisisobutyronitrile dissolved in 5.2 g of cyclohexanone was added dropwise over 30 minutes, and the mixture was further heated and stirred for 3 hours. The weight concentration of components other than cyclohexanone in the reaction solution was 28% by mass, and the molar amounts of 2-mercaptoethanol and α, α′-azobisisobutyronitrile were 2 mol% and 1%, respectively, with respect to the components other than cyclohexanone. Mol%.
After cooling to room temperature, 30 g of acetone was added to make a uniform solution, which was dropped into 2 L of hexane, and the resulting precipitate was collected by filtration and washed with hexane. The precipitate was dried under reduced pressure to obtain a polymer 1 (5.2 g, mass yield 91%) represented by the following structural formula (6).
The polymer 1 was confirmed to be the target compound by ¹ H NMR analysis, and it was found that the ratio of p and q in the following structural formula (6) was 1: 3.1.
The molecular weight of the obtained polymer 1 was calculated | required from the comparison with the GPC measurement result of the model polymer obtained by substituting the triethylamine salt of (p-vinylphenyl) trifluoromethanesulfonyl imido acid for the same reaction conditions. As a result of the GPC measurement, the polymer 1 had a weight average molecular weight (Mw) of 9056, a number average molecular weight (Mn) of 3904, and a molecular weight distribution (Mw / Mn) of 2.319.

(Synthesis of Colorant A)
0.8 g of the polymer 1 produced as described above is dissolved in 20 mL of acetone, and is a cationic dye represented by the following structural formula (7), Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. Was added while stirring at an equimolar amount with respect to the number of moles of the structural unit derived from the compound represented by the structural formula (5) calculated from the copolymerization ratio of the polymer 1, and further stirred at room temperature for 1 hour.
Acetone 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 precipitate was dried under reduced pressure to obtain 1.2 g (yield 67%) of Colorant A represented by the following structural formula (8). Colorant A was confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p and q in the following structural formula (8) was found to be 1: 2.9.

[Synthesis Example 3]
(Synthesis of polymer 2)
A polymer 2 represented by the structural formula (6) was obtained in the same manner as in Synthesis Example 2 except that the amount of glycidyl methacrylate in the synthesis of the polymer 1 was changed to 10.7 g (75 mmol).
The polymer 2 was confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p and q in the structural formula (6) was found to be 1: 10.5.
The molecular weight of the obtained polymer 2 was determined by comparing (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt with styrene and comparing with the GPC measurement results of the model polymer obtained under the same reaction conditions. As a result of the GPC measurement, the polymer 2 had a weight average molecular weight (Mw) of 9570, a number average molecular weight (Mn) of 4122, and a molecular weight distribution (Mw / Mn) of 2.322.

(Synthesis of Colorant B)
A colorant B represented by the structural formula (8) was obtained in a yield of 74% in the same manner as in Synthesis Example 2 except that the polymer 1 in the synthesis of the colorant A was changed to the polymer 2. Colorant B was confirmed to be the target compound by ¹ H NMR analysis, and it was found that the ratio of p and q in the structural formula (8) was 1:11.

[Synthesis Example 4]
(Synthesis of Polymer 3)
In the same manner as in Synthesis Example 2, except that the amount of glycidyl methacrylate used in the synthesis of polymer 1 was 5.4 g (38 mmol) and 5.7 g (57 mmol) of methyl methacrylate manufactured by Kanto Chemical Co., Inc. was added. A polymer 3 represented by the structural formula (9) was obtained.
The polymer 3 was confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p, q, and r in the following structural formula (9) was found to be 1: 5.1: 7.5. .
The molecular weight of the obtained polymer 3 was obtained from a comparison with the GPC measurement result of a model polymer obtained by replacing (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt with styrene and using the same reaction conditions. As a result of the GPC measurement, the polymer 3 had a weight average molecular weight (Mw) of 8,600, a number average molecular weight (Mn) of 3567, and a molecular weight distribution (Mw / Mn) of 2.412.

(Synthesis of Colorant C)
A colorant C represented by the following structural formula (10) was obtained in a yield of 74% in the same manner as in Synthesis Example 2 except that the polymer 1 in the synthesis of the colorant A was changed to the polymer 3.
The colorant C represented by the following structural formula (10) is confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p, q and r in the following structural formula (10) is 1: 5.5. : 7.3.

[Synthesis Example 5]
(Synthesis of macromonomer a)
A reaction vessel equipped with a cooling tube was charged with 80 g of cyclohexanone and heated to 90 ° C. while stirring under a nitrogen stream. A mixed solution of 100 g of methyl methacrylate, 4 g of 2-mercaptoethanol, 30 g of cyclohexanone, and 1 g of α, α′-azobisisobutyronitrile (abbreviation AIBN) was added dropwise over 1.5 hours, and the reaction was further performed for 3 hours. Next, the nitrogen stream was stopped, the reaction solution was cooled to 80 ° C., 8.74 g of methacryloyloxyethyl isocyanate (trade name; Karenz MOI) manufactured by Showa Denko KK, 0.125 g of tin octylate, p- By adding 0.125 g of methoxyphenol and 20 g of cyclohexanone and stirring for 3 hours, a 47.4% solution of macromonomer a was obtained.
When the molecular weight of the obtained macromonomer a was confirmed by GPC measurement under the conditions of N-methylpyrrolidone, 0.01 mol / L lithium bromide added / polystyrene standard, the weight average molecular weight (Mw) was 3,539. The average molecular weight (Mn) was 1573, and the molecular weight distribution (Mw / Mn) was 2.24.

(Synthesis of polymer 4)
A reaction vessel equipped with a cooling tube was charged with 12.5 g of cyclohexanone, 13.3 g of macromonomer a solution (effective solid content 6.3 g), 3.56 g (25 mmol) of glycidyl methacrylate, obtained in Synthesis Example 1 (p- Vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt 2.0 g (5.0 mmol) and 2-mercaptoethanol 129 mg (1.65 mmol) were added. While stirring this mixture, the temperature was raised to 100 ° C., 12.5 g of cyclohexanone, 13.3 g of macromonomer a solution (effective solid content 6.3 g), 3.56 g (25 mmol) of glycidyl methacrylate, (p-vinylphenyl) ) A mixed solution of 2.0 g (5.0 mmol) of trifluoromethanesulfonylimidic acid triethylamine salt, 129 mg (1.65 mmol) of 2-mercaptoethanol, and 272 mg (1.63 mmol) of α, α′-azobisisobutyronitrile. After dropwise addition over 5 hours and heating and stirring for 3 hours, a mixed solution of 30 mg (0.16 mmol) of α, α′-azobisisobutyronitrile and 3 g of cyclohexanone was added dropwise over 10 minutes. Aged for 1 hour.
After cooling to room temperature, 30 g of acetone was added to make a uniform solution, which was dropped into 2 L of hexane, and the resulting precipitate was collected by filtration and washed with hexane. The precipitate was dried under reduced pressure to obtain polymer 4 (20.4 g, mass yield 88%) represented by the following structural formula (11).
The polymer 4 was confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p, q and r in the following structural formula (11) was found to be 1: 4.0: 0.8. .
The molecular weight of the obtained polymer 4 was obtained from a comparison with the GPC measurement result of a model polymer obtained by replacing (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt with styrene and using the same reaction conditions. As a result of the GPC measurement, the polymer 4 had a weight average molecular weight (Mw) of 9521, a number average molecular weight (Mn) of 4374, and a molecular weight distribution (Mw / Mn) of 2.177.

(Synthesis of Colorant D)
A colorant D represented by the following structural formula (12) was obtained at a yield of 78% in the same manner as in Synthesis Example 2 except that the polymer 1 in the synthesis of the colorant A was changed to the polymer 4. The colorant D represented by the following structural formula (12) is confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p, q and r in the following structural formula (12) is 1: 4.0: It was found to be 0.6.

[Synthesis Example 6]
(Synthesis of Colorant E)
1. 85 g (3.60 mmol) of Basic Blue 7 (CI-42595) manufactured by Tokyo Chemical Industry Co., Ltd. represented by the structural formula (7) was dissolved in 30 mL of methanol, and the structural formula ( While stirring the (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt represented by 5), 1.31 g (3.60 mmol) was added, 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 precipitate was dried under reduced pressure to obtain 2.33 g (yield 82%) of a colorant E represented by the following structural formula (13). The colorant E represented by the following structural formula (13) was confirmed to be the target compound from the following analysis results.
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%)

[Synthesis Example 7]
(Synthesis of polymer 5)
2.2 g (5.5 mmol) of (p-vinylphenyl) trifluoromethanesulfonylimidic acid triethylamine salt obtained in Synthesis Example 1 was dissolved in 5 g of cyclohexanone. To this product, 8.5 mg (0.11 mmol) of 2-mercaptoethanol was added, and then heated to 100 ° C. and stirred. While stirring, a solution prepared by dissolving 9.0 mg (0.055 mmol) of α, α′-azobisisobutyronitrile in 3 g of cyclohexanone was added dropwise over 20 minutes, and the mixture was further heated and stirred for 3 hours.
After cooling to room temperature, 8 g of acetone was added to make a uniform solution, which was dropped into 1 L of hexane, and the resulting precipitate was collected by filtration and washed with hexane. The precipitate was dried under reduced pressure to obtain polymer 5 (1.8 g, mass yield 82%) represented by the following structural formula (14).
The polymer 5 represented by the following structural formula (14) was confirmed to be the target compound by ¹ H NMR analysis.
The obtained polymer 5 was calculated | required from the comparison with the GPC measurement result of the model polymer obtained by substituting the styrene for the (p-vinylphenyl) trifluoromethanesulfonyl imido acid triethylamine salt, and the same reaction conditions. As a result of the GPC measurement, the polymer 5 had a weight average molecular weight (Mw) of 3023, a number average molecular weight (Mn) of 1500, and a molecular weight distribution (Mw / Mn) of 2.015.

(Synthesis of Colorant F)
A colorant F represented by the following structural formula (15) was obtained in a yield of 84% in the same manner as in Synthesis Example 2 except that the polymer 1 in the synthesis of the colorant A was changed to the polymer 5. The coloring agent F shown by following Structural formula (15) has confirmed that it was the target compound from < ¹ > H NMR analysis.

[Synthesis Example 8]
(Synthesis of polymer 6)
A polymer 6 represented by the following structural formula (16) was obtained in the same manner as in Synthesis Example 2 except that glycidyl methacrylate in the synthesis of the polymer 1 was changed to methyl methacrylate. The polymer 6 was confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p and r in the following structural formula (16) was found to be 1: 2.0.
The obtained polymer 6 was calculated | required from the comparison with the GPC measurement result of the model polymer obtained by substituting the styrene for the (p-vinylphenyl) trifluoromethanesulfonyl imido acid triethylamine salt, and the same reaction conditions. As a result of the GPC measurement, the polymer 6 had a weight average molecular weight (Mw) of 7659, a number average molecular weight (Mn) of 3267, and a molecular weight distribution (Mw / Mn) of 2.344.

(Synthesis of Colorant G)
A colorant G represented by the following structural formula (17) was obtained in a yield of 74% in the same manner as in Synthesis Example 2 except that the polymer 1 in the synthesis of the colorant A was changed to the polymer 6. The colorant G represented by the following structural formula (17) is confirmed to be the target compound by ¹ H NMR analysis, and the ratio of p and r in the following structural formula (17) is 1: 1.6. I understood.

[Preparation Example 1]
(Preparation of photosensitive transparent resin composition 1)
A photosensitive transparent resin composition 1 having a nonvolatile component of 40% by mass and 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 mg KOH / g, weight average molecular weight: 9000, PGMEA = propylene glycol monomethyl ether acetate ): 21 parts by mass. Multifunctional acrylate monomer (dipentaerythritol penta and hexaacrylate (trade name; Aronix M403, manufactured by Toagosei Co., Ltd.)): 4.8 parts by mass. Photopolymerization initiator (2-methyl-1) [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (trade name; Irgacure 907, manufactured by BASF Corporation)): 2 parts by mass / photosensitizer (4,4′-dimethyl) Aminobenzophenone): 0.25 parts by mass

[Example 1]
(Preparation of coloring composition 1 for color filter)
The following components were mixed and stirred to prepare a colored composition 1 for a color filter having a non-volatile component of 20% by mass.
-10% by weight of cyclohexanone solution of Colorant A: 15 parts by weight-Photosensitive transparent resin composition 1: 10 parts by weight-Fluorine-based additive (trade name; Megafac R-08MH, manufactured by DIC Corporation): 0 .02 parts by mass

(Evaluation 1: Evaluation of NMP resistance, heat resistance and contrast)
Using the above color filter coloring composition 1 as a coating liquid, this was applied onto a glass substrate by spin coating, dried at 80 ° C., and exposed to 100 mJ / m ^{2 of} ultraviolet light with a high-pressure mercury lamp from the coating film side. A coating film for evaluation was prepared by curing. Using this coating film, NMP resistance, heat resistance and contrast 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 a high pressure mercury lamp and then sufficiently cured by heating at 230 ° C. for 30 minutes.
For NMP resistance, 1 drop of NMP is dropped on the surface of the coating film on the glass substrate, left to stand for 5 minutes, and then wiped with a wipe (trade name: Bencott Lint Free AZ-8, manufactured by Gardner) before and after dropping NMP. The coating film spectrum, ie, ΔEab value, was measured using an Olympus Co., Ltd. microspectrophotometer “OSP-SP200” and evaluated by calculating the color difference. The smaller the color difference, the less elution by NMP and the higher the resistance to NMP.

-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 100 mJ / m ² with a high-pressure mercury lamp. Next, the glass substrate was left at 200 ° C. for 30 minutes. 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.

-Contrast evaluation-
In the same manner as in the section for evaluation of heat resistance, the glass substrate was allowed to stand at 200 ° C. for 30 minutes, and the contrast value of the produced glass substrate was measured using a contrast measuring device “CT-1B” manufactured by Aisaka Electric Co., Ltd. As the obtained contrast value is larger, the degree of light scattering is smaller, the leakage light when used as a color filter of a liquid crystal display device is reduced, and the brightness and darkness of the liquid crystal panel can be made clear.
In order to increase the contrast value, the coating film is required to be uniform. In a non-uniform coating film in which crystal precipitation or phase separation has occurred, the contrast value becomes small.

(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.
<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 this evaluation, it can be evaluated that the electrical reliability is high when the voltage holding ratio is 80% or more.
In addition, the coating film which consists of the coloring composition for color filters used for the said electrical reliability evaluation was specifically produced with the following method.

<Method for producing coating film>
The colored composition for a color filter 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 coloring composition for color filters was produced.

[Example 2]
A color filter coloring composition 2 was prepared in the same manner as in Example 1 except that the colorant A in the color filter coloring composition 1 was changed to the colorant B and the blending amount thereof was as follows.
10% by mass of Colorant B in cyclohexanone solution: 20 parts by mass Photosensitive transparent resin composition 1: 10 parts by mass 0.02 part by mass Using the prepared colored composition 2 for color filter, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
A color filter coloring composition 3 was prepared in the same manner as in Example 2 except that the colorant B in the color filter coloring composition 2 was changed to the colorant C.
Evaluation was performed in the same manner as in Example 1 by using the prepared colored composition 3 for a color filter. The results are shown in Table 1.

[Example 4]
A color filter coloring composition 4 was prepared in the same manner as in Example 2 except that the colorant B in the color filter coloring composition 2 was changed to the colorant D.
Evaluation was performed in the same manner as in Example 1 by using the prepared colored composition 4 for a color filter. The results are shown in Table 1.

[Example 5]
The following components were mixed and stirred to prepare a colored composition 5 for a color filter having a nonvolatile component of 20% by mass.
-PGMEA solution of 10% by weight of Colorant D: 12 parts by weight-10% by weight Dispersed pigment liquid: 8 parts by weight-Photosensitive transparent resin composition 1: 10 parts by weight-Fluorine-based additive (trade name; Megafak R -08MH, manufactured by DIC Corporation): 0.02 parts by mass / PGMEA
In addition, the dispersed pigment liquid is C.I. I. Pigment Blue 15: 6 is 22 parts by mass, Disperbyk-2001 (produced by Big Chemie) as a dispersant is 18 parts by mass (in terms of solid content), and 60 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) is processed as a solvent by a bead mill. Then, PGMEA mixed so as to have the above-mentioned mass% was used.
Evaluation was performed in the same manner as in Example 1 using the prepared colored composition 5 for a color filter. The results are shown in Table 1.

[Comparative Example 1]
A color filter coloring composition 6 was prepared in the same manner as in Example 1, except that the colorant A in the color filter coloring composition 1 was changed to the colorant E and the blending amount thereof was as follows.
10% by mass of cyclohexanone solution of colorant E: 10 parts by mass Photosensitive transparent resin composition 1: 20 parts by mass Fluorine-based additive (trade name; Megafac R-08MH, manufactured by DIC Corporation): 0 0.02 parts by mass Using the prepared colored composition 6 for a color filter, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
A color filter coloring composition 7 was prepared in the same manner as in Comparative Example 1 except that the colorant E in the color filter coloring composition 6 was changed to the colorant F.
Evaluation was performed in the same manner as in Example 1 using the prepared colored composition 7 for a color filter. The results are shown in Table 1.

[Comparative Example 3]
A color filter coloring composition 8 was prepared in the same manner as in Example 1 except that the colorant A in the color filter coloring composition 1 was changed to the colorant G.
Evaluation was performed in the same manner as in Example 1 using the prepared colored composition 8 for a color filter. The results are shown in Table 1.

As shown in the results of Table 1, the coloring compositions for color filters of Examples 1 to 5 are (A) a cationic dye represented by the general formula (I), and (B) the general formula (II). And since it uses the coloring agent AD containing the polymer containing the structural unit derived from the compound represented by (III), all are excellent in NMP tolerance and electrical reliability compared with Comparative Examples 1-3. I understand that.
In addition to the structural unit derived from the compounds represented by the general formulas (II) and (III) as a structural unit of the component (B), methyl which is a compound containing a functional group having an ethylenically unsaturated bond In Examples 3 to 5 including a structural unit derived from a methacrylate or a macromonomer, it can be seen that a higher contrast is obtained and heat resistance is superior as compared to Examples 1 and 2 that do not include the structural unit. In particular, in Examples 4 and 5 in which a macromonomer is used as a compound containing a functional group having an ethylenically unsaturated bond, the above effect is remarkably observed.

On the other hand, in Comparative Example 1 using a colorant composed of (A) a cationic dye and an anionic compound represented by the general formula (II), the contrast and heat resistance are good, but NMP resistance and electricity The reliability is low, and as shown in Comparative Example 2, even when the anionic compound of Comparative Example 1 is used as a polymer, the above characteristics are not improved.
In Comparative Example 3, the polymer (B) is composed of a structural unit derived from the anionic compound represented by the general formula (II) and a structural unit derived from methyl methacrylate. Since the structural unit derived from the compound represented by the general formula (III) is not included, NMP resistance and electrical reliability are reduced as compared with Examples 1-5.

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 (11)

A binder resin, a crosslinkable monomer, a photopolymerization initiator, a colorant and a solvent, wherein the colorant is (A) a cationic dye represented by the following general formula (I), and (B) the following general formula (II The coloring composition for color filters containing the polymer containing the structural unit derived from the anionic compound represented by the following, and the structural unit derived from the compound represented by the following general formula (III).

Wherein (I), R ¹ ~R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group, or an aryl group which may have a substituent, R ¹ And R ² , R ³ and R ⁴ , and R ⁵ and R ⁶ may be bonded to each other to form a part of a ring structure or a heterocyclic structure. ]

[In formula (II), R ⁷ represents a hydrogen atom or a methyl group. X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, and Y represents a divalent organic group. ]

[In formula (III), R ⁸ represents a hydrogen atom or a methyl group. A represents a divalent organic group. ]   The component (B) is a structural unit derived from the anionic compound represented by the general formula (II), a structural unit derived from the compound represented by the general formula (III), and an ethylenically unsaturated bond. The coloring composition for a color filter according to claim 1, wherein the coloring composition is a polymer composed of a structural unit derived from a compound having a functional group.   The coloring composition for color filters according to claim 2, wherein at least one of the compounds containing a functional group having an ethylenically unsaturated bond is a macromonomer. The coloring composition for a color filter according to claim 3, wherein the macromonomer includes a structural unit represented by the following general formula (IV) and / or (V).

[In formula (IV), R ⁹ represents a hydrogen atom or a methyl group, R ¹⁰ represents an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ¹¹ ) —CH (R ¹² ) —O] _a —R ¹³ , — [(CH ₂ ) _b —O] _c —R ¹³ , — [CO— (CH ₂ ) _b —O] _c —R ¹³ , —CO—O—R ¹⁴ or a monovalent group represented by —O—CO—R ¹⁵ .
R ¹¹ and R ¹² each independently represent a hydrogen atom or a methyl group.
R ¹³ is a hydrogen atom or a monovalent group represented by an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ¹⁶ , and R ¹⁶ is a hydrogen atom An atom or an alkyl group having 1 to 5 carbon atoms is shown.
R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms, an aralkyl group, an aryl group, a cyano group, — [CH (R ¹¹ ) —CH (R ¹² ) —O] _a —R ¹³ , — [(CH ₂ ) _b A monovalent group represented by —O] _c —R ¹³ or — [CO— (CH ₂ ) _b —O] _c —R ¹³ ;
R ¹⁵ represents an alkyl group having 1 to 18 carbon atoms.
The alkyl group, aralkyl group, or aryl group contained in R ¹⁰ may have a substituent.
k represents an integer of 5 to 200. a represents an integer of 1 to 18, b represents an integer of 1 to 5, and c represents an integer of 1 to 18. ]

[In the formula (V), m represents an integer of 1 to 5, and n represents an integer of 5 to 200. ]   The macromonomer has a structure in which a functional group having an ethylenically unsaturated bond and a structural unit represented by the general formula (IV) or (V) are linked via a divalent organic group. Item 5. A coloring composition for a color filter according to Item 4.   The coloring composition for a color filter according to any one of claims 2 to 5, wherein the functional group having an ethylenically unsaturated bond is a (meth) acryloyl group, a vinyl group, or an allyl group.   The coloring composition for a color filter according to any one of claims 1 to 6, wherein X in the general formula (II) 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 an alkyl group having 1 to 20 carbon atoms. The coloring composition for a color filter according to item 1.   Furthermore, the coloring composition for color filters of any one of Claims 1-8 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 9.   A liquid crystal display device comprising: the color filter according to claim 10; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.

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