JP2007071924A - Color composition for color filter, and the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color composition for a color filter having low viscosity and superior dispersion stability, even if the composition contains a pigment at a high concentration, particularly, showing proper storage stability or the like, and giving high contrast, and to provide a color filter having high contrast. <P>SOLUTION: The composition for a color filter contains a pigment carrier, comprising at least a transparent resin, its precursor or the mixture of these, an organic pigment and a compound expressed by general Formula (1). The color filter has a filter segment formed of this color composition. In the Formula (1), X represents O or NH, each of R<SB>1</SB>to R<SB>4</SB>independently represents a hydrogen atom, halogen atom, nitro group, sulfonic acid group, carboxyl group, formyl group, or alkyl group, aryl group, alicyclic group, aralkyl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, dialkylamino group or the like which may have a substituent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coloring composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged in a fixed arrangement. It is made up of arranged ones. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
On the color filter used in the color liquid crystal display device, a transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. Has been. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

Therefore, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used. The color filter is mainly produced by the following two methods. Is manufactured.
In the first method, a photosensitive coloring composition in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and after removing the solvent by drying, pattern exposure of one filter color is performed. Next, the unexposed area is removed in the development process to form a pattern of the first color, and a process such as heating is applied as necessary, and then the same operation is sequentially repeated for all filter colors to produce a color filter. is there.

  In the second method, a colored composition in which a pigment is dispersed in a transparent resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying to form a pigment-dispersed coating film. A resist such as a mold resist is applied, pattern exposure of one filter color is performed, a resist pattern is formed by development, and this is used as an etching resist to remove the pigment-dispersed coating film with no resist pattern attached with an etching solution Then, the resist coating film is peeled off to form a first color pattern. This is a method for producing a color filter by repeating the same operation for all the filter colors in sequence after applying heat treatment or the like as necessary. The resist development and the pigment-dispersed coating film etching can be performed simultaneously.

In the production of such a color filter, the dispersibility of the pigment in the colored composition is important. When a color filter is produced using a colored composition with low dispersibility, the hue is poor, the contrast is decreased, the viscosity is increased, etc. Cause.
Therefore, it has been proposed to add a compound having an isoindoline skeleton described in Patent Document 1 to the coloring composition as a pigment dispersant. However, although the compound having an isoindoline skeleton described in Patent Document 1 has a dispersion effect on the isoindoline pigment, the effect is slight and the required low viscosity cannot be achieved. Therefore, the development of a more effective dispersant has been an issue.
JP 63-161061 A

As described above, in the situation where there is an increasing demand for the physical properties of the coloring composition used in the production of the color filter, such as dispersion stability, storage stability, and coating uniformity when forming the filter segment, Conventionally used pigment dispersants have become difficult to cope with. In particular, in recent years, liquid crystal display devices have been applied to television monitor applications, and high-density color filters containing a large amount of pigment are required to produce panels.
Accordingly, the present invention provides a coloring composition for a color filter that has a low viscosity even when containing a high concentration of pigment, is excellent in dispersion stability, particularly has good storage stability, and provides high contrast, and An object of the present invention is to provide a color filter having a high contrast by forming a filter segment.

（式中、Ｘは、Ｏ、またはＮＨを表す。Ｒ₁〜Ｒ₄はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよい脂環基、置換基を有してもよいアラルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいジアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいジアリールアミノ基、ハロゲン原子、ニトロ基、スルホン酸基、カルボキシル基、ホルミル基、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルホンアミド基を表す。）
また、本発明のカラーフィルタは、上記着色組成物から形成されるフィルタセグメントを具備することを特徴とする。 The coloring composition for a color filter of the present invention contains at least a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, an organic pigment, and a compound represented by the following general formula (1). And

(In the formula, X represents O or NH. R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alicyclic group which may have a group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and a substituent Aryloxy group which may have a substituent, alkylthio group which may have a substituent, arylthio group which may have a substituent, alkylamino group which may have a substituent, dialkyl which may have a substituent An amino group, an arylamino group which may have a substituent, a diarylamino group which may have a substituent, a halogen atom, a nitro group, a sulfonic acid group, a carboxyl group, a formyl group, or a substituent A good phthalimidomethyl group or an optionally substituted substituent It represents a Hon'amido group.)
Moreover, the color filter of this invention comprises the filter segment formed from the said coloring composition, It is characterized by the above-mentioned.

The coloring composition for a color filter of the present invention contains a compound represented by the above general formula (1) having a function of stably dispersing fine particles of an organic pigment in a pigment carrier, and therefore, dispersion stability, particularly storage stability. The coating film formed using the coloring composition has excellent contrast and high contrast.
And the color filter which comprises a filter segment with high contrast can be manufactured by using the coloring composition for color filters of this invention.

First, the coloring composition for a color filter of the present invention will be described.
The coloring composition for a color filter of the present invention comprises at least a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, an organic pigment, and a compound represented by the above general formula (1). To do.
Among the compounds represented by the above general formula (1), the compound in which X is NH is a cyanomethyl amidomethyl and 1,3-diiminoisoindoline compound at a pH of 8 to 11 and a temperature of 10 to 100 ° C. It can synthesize | combine by making it react under.
In addition, among the compounds represented by the general formula (1), a compound in which X is O can be obtained by heating a compound in which X is NH, for example, in an acetic acid aqueous solution.

Here, when it illustrates about R < ₁ > -R < ₄ > in General formula (1), there exist a fluorine, chlorine, a bromine, an iodine etc. as a halogen atom in R < ₁ > -R < ₄ > in General formula (1).
Examples of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, and stearyl. Group, 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2- There are ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group and the like.
As the aryl group which may have a substituent, phenyl group, naphthyl group, anthranyl group, p-methylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl Group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group And 2-aminoanthraquinolyl group.

Examples of the alicyclic group which may have a substituent include a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a cyclohexyl group, a 4-tert-butylcyclohexyl group and an adamantyl group.
Examples of the aralkyl group which may have a substituent include a benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like. There is.
Examples of the heterocyclic group that may have a substituent include a pyridinyl group, a 3-methylpyridinyl group, a pyrazinyl group, a pipedinyl group, an N-methylpipedinyl group, a pyranyl group, a morpholinyl group, an n-methylpyrrolinyl group, and an acridinyl group. is there.
Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, and an n-hexyloxy group. , N-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group and the like.

As the aryloxy group which may have a substituent, a phenoxy group, a naphthoxy group, an anthranyloxy group, a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, Examples include pentafluorophenoxy group and 2-methyl-4-chlorophenoxy group.
Examples of the alkylthio group which may have a substituent include methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylo group, tert-butylthio group, neopentylthio group, n-hexylthio group, n -There is an octylthio group.
Examples of the arylthio group which may have a substituent include a phenylthio group, a naphthylthio group, a p-methylphenylthio group, a p-nitrophenylthio group, and a p-methoxyphenylthio group.

Examples of the alkylamino group which may have a substituent include a methylamino group and an ethylamino group.
Examples of the dialkylamino group which may have a substituent include a dimethylamino group, a dimethylamino group, a diisopropyl group, and a cyclohexylamino group.
Examples of the arylamino group which may have a substituent include a phenylamino group, a p-nitrophenylamino group, and a 4-methylphenylamino group.
Examples of the diarylamino group which may have a substituent include a diphenylamino group and a di (4-methoxyphenyl) amino group.
Examples of the phthalimidomethyl group which may have a substituent include a 4-nitrophthalimidomethyl group and a tetrachlorophthalimidomethyl group.
R _{1 to} R ₄ are not limited to these.

As a method for introducing a substituent into R _{1 to} R ₄ , for example, the following known methods can be used.
Substituted by a well-known synthetic method that converts phthalic acid to phthalic anhydride, phthalimide, phthalamide, and phthalonitrile in order, starting from nitrophthalic acid, halogenated phthalic anhydride, and trimellitic anhydride, which are commercially available. A compound of the general formula (1) having a nitro group, a halogen atom or a carboxyl group can be obtained by synthesizing a phthalonitrile having a group and reacting it with amide methyl cyanoacetate.
Also, by synthesizing phthalonitrile having a nitro group with alcohols, thiols, phenols, thiophenols to synthesize phthalonitrile having a substituent, and reacting this with amide methyl cyanoacetate, Of the general formula (1) having an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, and an arylthio group which may have a substituent A compound can be obtained.
In addition, using commercially available o-xylene as a raw material, various alkyl groups are introduced into the benzene ring by known Friedel-Crafts reaction, and the methyl group is oxidized to form phthalic anhydride, phthalimide from phthalic acid. , Phthalamide and phthalonitrile are synthesized by a known synthesis method in order to synthesize phthalonitrile having a substituent and react this with cyanomethyl amidoacetate to obtain an alkyl group which may have a substituent. The compound of the general formula (1) having can be obtained.

As the organic pigment contained in the color filter coloring composition of the present invention, commercially available ones can be used, and dyes, natural pigments, and inorganic pigments are used in combination according to the hue of the filter segment to be formed. be able to. Among them, when a pigment having the same or similar chemical structure as the compound represented by the general formula (1) is used, the effect of improving non-aggregability, non-crystallinity, fluidity and the like is great. Specific examples thereof include isoindolinone pigments (for example, CI Pigment Yellow 109, 110, 173), isoindoline pigments (for example, CI Pigment Yellow 139, 185), and the like. In particular, when CI Pigment Yellow 185 pigment having the same chemical structure is used, the effect is great. Further, when a quinophthalone pigment (CI Pigment Yellow138) is used, the effect is high, and it is advantageous in that the hue of the pigment is not changed.
As the organic pigment, those having high color developability and high heat resistance are preferably used. An organic pigment etc. can be used individually or in mixture of 2 or more types. Further, the organic pigment may be refined by salt milling, acid pasting or the like.
Below, the specific example of the organic pigment which can be used for the coloring composition for color filters of this invention is shown with a color index number.

When forming a red filter segment from the coloring composition for a color filter of the present invention, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81 : 2, 81: 3, 146, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272 and the like can be used. Of these, CI Pigment Red 48: 3, 254 is preferred. A yellow pigment exemplified later can be used in combination with the red pigment.
When forming a green filter segment from the coloring composition for a color filter of the present invention, green pigments such as CI Pigment Green 7, 10, 36, and 37 can be used. Of these, CI Pigment Green 36 is preferred. A yellow pigment exemplified later can be used in combination with the green pigment.
When forming a blue filter segment from the coloring composition for a color filter of the present invention, blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 80, etc. Can be used. Of these, CI Pigment Blue 15: 6 is preferable. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination with the blue pigment. Among these, CI Pigment Violet 23 is preferable.

  When forming a yellow color filter segment from the coloring composition for a color filter of the present invention, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 It can be used yellow pigments such 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,198,213,214.

When forming a magenta color filter segment from the coloring composition for a color filter of the present invention, CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, Pigments such as 81: 2, 81: 3, 146, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272 can be used.
When forming a cyan filter segment from the coloring composition for a color filter of the present invention, pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 80, etc. Can be used.
The coloring composition for a color filter of the present invention has titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness. Inorganic pigments such as zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black can be included.

  In the coloring composition for a color filter of the present invention, the compound represented by the general formula (1) is preferably contained at a ratio of 5 to 20 parts by weight with respect to 100 parts by weight of the organic pigment, and from the viewpoint of storage stability. From 5 to 10 parts by weight based on 100 parts by weight of the organic pigment is more preferable. If the content of the compound represented by the general formula (1) is less than the above range, the pigment dispersion stabilizing effect is not sufficiently exhibited. Conversely, if the content is more than the above range, the hue of the filter segment is unfavorable. The possibility of change arises, and the production cost is also a problem.

As described above, the pigment carrier in which the organic pigment and the compound represented by the general formula (1) are dispersed is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Alternatively, two or more kinds can be mixed and used.
When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator or the like is added to the coloring composition for a color filter of the present invention.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like.
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.
The content of the transparent resin is preferably 30 to 700 parts by weight and more preferably 60 to 450 parts by weight with respect to 100 parts by weight of the organic pigment. If the content of the transparent resin is less than 30 parts by weight, the developing performance is lowered, and if it exceeds 700 parts by weight, it is not preferable from the viewpoint of causing curability of the coloring composition and poor hue.

Monomers and oligomers that are precursors of transparent resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, various acrylic esters such as epoxy (meth) acrylate and methacrylic acid Examples include esters, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile.
The content of the monomer and oligomer is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the organic pigment, more preferably 10 to 200 parts by weight from the viewpoint of photocurability and developability. Particularly preferred is 15 to 150 parts by weight. When the content of the monomer and oligomer is more than 300 parts by weight, it is not preferable because the shape of the filter segment is poor.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4'-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used. .
The content of the photopolymerization initiator used in the color filter coloring composition is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the organic pigment, and is 10 to 10 from the viewpoint of photocurability and developability. More preferably, it is 150 parts by weight. When the content of the photopolymerization initiator is more than 200 parts by weight, it is not preferable because the shape of the filter segment is poor, and when it is less than 5 parts by weight, the photocurability is insufficient.

The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
The content of the sensitizer used in the color filter coloring composition is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the color composition, and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50 parts by weight. When the content of the sensitizer is less than 3 parts by weight, it is not preferable because sufficient photocurability may not be obtained. .

  The coloring composition for a color filter of the present invention is a method of dispersing an organic pigment in a pigment carrier solution, or a method of mixing an organic pigment in water or an organic solvent to prepare a pigment dispersion and then mixing with the pigment carrier solution. Manufactured by. The method for dispersing the pigment is not particularly limited, but a method using a bead mill, a sand mill, a ball mill, a three roll mill, a two roll mill or the like is preferable. The organic pigment and the compound represented by the general formula (1) can be separately dispersed in the pigment carrier solution and then mixed. However, in order to improve the dispersibility of the organic pigment, the organic pigment is dispersed. It is preferable to add a compound represented by the general formula (1).

When the coloring composition for color filter contains two or more kinds of pigments, etc., the coloring composition is mixed with two or more kinds of pigments, and then the resulting pigment mixture is finely divided in a pigment carrier by a known method. It can be dispersed and manufactured. Moreover, the coloring composition for color filters can also be produced by mixing finely dispersed pigments in a pigment carrier.
When the organic pigment is dispersed in the pigment carrier, a dispersion aid such as a surfactant or a dye derivative can be appropriately used. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight with respect to 100 parts by weight of the organic pigment.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene ether Nonionic surfactants such as kill ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines. These can be used alone or in admixture of two or more.

Moreover, the coloring composition for color filters of this invention can contain a pigment derivative and / or a dispersing agent.
The pigment derivative is a compound represented by the following general formula (2), and there are those having a basic substituent and those having an acidic substituent.
Formula (2)
AB
A: Organic pigment residue B: Basic substituent or acidic substituent

  In formula (2), examples of the organic pigment constituting the organic pigment residue of A include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine. Phthalocyanine pigments, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo Pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.

式（４）

式（５）

式（６）

In the formula (2), examples of the basic substituent of B include substituents represented by the following formula (3), formula (4), formula (5), and formula (6). , Substituents represented by formula (7), formula (8), and formula (9).
Formula (3)

Formula (4)

Formula (5)

Formula (6)

式（８）

式（９）

Formula (7)

Formula (8)

Formula (9)

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R ₁ and R ₂ together represent an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ , R ₇ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituent Represents an optionally substituted phenyl group.

Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents.
Z: represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.
R: represents a substituent represented by the formula (10) or a substituent represented by the formula (11).
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (10) or a substituent represented by the formula (11).

式（１１）

Formula (10)

Formula (11)

M: represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom or aluminum atom.
i: represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, substitution Represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used to form the substituents represented by formula (3) to formula (6), formula (10), and formula (11) include dimethylamine, diethylamine, N, N-ethylisopropyl, and the like. Amine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine N, N-methyloctadecylamine, didecyl Min, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N -Diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N Methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, Pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl- 4-Pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like can be mentioned.

  The amine component used to form the sulfonic acid amine salt of formula (9) may be any of primary, secondary, tertiary and quaternary amines. For example, primary amines have side chains. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, Examples include amines such as eocosylamine, or unsaturated amines corresponding to the number of carbon atoms.

Secondary, tertiary and quaternary amines include dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldidodecylammonium chloride, Dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl tetradecyl ammonium chloride , Dimethyl hexadecyl octadec Ammonium chloride, and the like.
Further, when any of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in the formula (9) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group and a polyoxypropylene group.

  Furthermore, in the coloring composition for a color filter of the present invention, an organic pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as a glass substrate so that the dry film thickness is 1 to 2.5 μm. A solvent can be included to facilitate forming the filter segment. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the organic pigment.

  The coloring composition for color filter of the present invention can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The colored resist material is composed of a pigment carrier, a thermosetting resin, a thermoplastic resin or a photosensitive resin and a monomer, and if necessary, a composition containing a photopolymerization initiator, an organic pigment, and a general formula (1) The compound shown is dispersed.

The organic pigment is preferably contained in a coloring composition containing a solvent in a ratio of 1 to 7% by weight when the filter segment is formed by a photolithography method, and when the filter segment is formed by a printing method. In the coloring composition containing a solvent, it is contained in a proportion of 1 to 50% by weight. In any case, the organic pigment is preferably contained in the final filter segment (solid content of the coloring composition) in a proportion of 10 to 55% by weight, more preferably 20 to 50% by weight, with the remainder depending on the pigment carrier. It consists essentially of the resinous binder provided.
The colored composition for a color filter of the present invention is a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a particle of 0.5 μm or more by means of centrifugation, a sintered filter, a membrane filter or the like. It is preferable to remove the mixed dust.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises one or a plurality of color filter segments formed using the colored composition for color filter of the present invention on a transparent or reflective substrate. ), G (green), and B (blue) filter segments, and Y (yellow), M (magenta), and C (cyan) filter segments. . The filter segment of each color can be formed by a printing method or a photolithography method.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When each color filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied to a transparent or reflective substrate by spray coating, spin coating, slit coating, roll coating. With a coating method such as the above, the coating is applied so that the dry film thickness is 0.2 to 5 μm, and is dried as necessary to form a pigment-dispersed coating film. Next, ultraviolet exposure is performed through a mask having a predetermined pattern in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

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

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the color filter coloring composition of the present invention can be used in any method. The electrodeposition method uses a transparent conductive film formed on a transparent or reflective substrate to produce a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. Is the method.
The transfer method is a method in which a colored composition layer is previously formed on the surface of a peelable transfer base sheet, and the colored composition layer is transferred to a desired transparent or reflective substrate.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
The color filter and the counter substrate are bonded together using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by pasting together.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically compensated bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

  Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Production Example 1)
10 parts of a 40% methylamine methanol solution were added to 14.7 parts of ethyl cyanoacetate, and the mixture was heated and stirred at the boiling point for 2 hours. After cooling to 50 ° C., 300 parts of methanol and 19 parts of 1,3-diiminoisoindoline were added, and the mixture was further stirred at 50 ° C. for 2 hours, and then cooled to room temperature. Washing was performed 3 times with 100 parts of methanol to obtain a compound (A) having the following structure.

(Production Example 2)
To 30 parts of the compound (A) obtained in Production Example 1, 1000 parts of a 60% aqueous acetic acid solution was added, stirred at the boiling point for 5 hours, and cooled to room temperature. After washing with water, a compound (B) having the following structure was obtained.

The compounds obtained in Production Examples 1 and 2 were identified by ¹ H-NMR and LC / MS, and it was confirmed that the target compounds were obtained.
(Preparation of acrylic resin solution)
Put 800 parts of cyclohexanone in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate from the dropping tube. A mixture of 60.0 parts of 2-hydroxyethyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain a weight average molecular weight. A solution of about 40,000 acrylic resin was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

(Preparation of yellow-treated pigment 1)
500 parts of CI Pigment Yellow 185 ("Pariotor Yellow D1155" manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C for 2 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow-treated pigment 1 were obtained.
(Preparation of yellow-treated pigment 2)
490 parts of yellow-treated pigment 2 were obtained in the same manner as in Preparation 1 of yellow-treated pigment, except that CI Pigment Yellow 185 was changed to CI Pigment Yellow 139 ("Pariotor Yellow D1819" manufactured by BASF).
(Preparation of green processing pigment)
490 parts of green-treated pigment was obtained in the same manner as in Preparation 1 of yellow-treated pigment except that CI Pigment Yellow 185 was changed to CI Pigment Green 7 (“LIONOL GREEN YS” manufactured by Toyo Ink Manufacturing Co., Ltd.).

[Examples 1-8 and Comparative Examples 1-3]
After the mixture having the composition shown in Table 1 was uniformly stirred and mixed, it was dispersed with an Eiger mill for 3 hours using zirconia beads having a diameter of 1 mm, and filtered with a 5 μm filter to prepare a pigment dispersion. A mixture of the following composition containing the obtained pigment dispersion was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an alkali developing type colored resist material.
Pigment dispersion 60.0 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba) 1.2 parts Trimethylolpropane triacrylate 4.2 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part Acrylic resin solution 11.0 part Cyclohexanone 23.2 parts

*１：実施例および比較例に用いられた顔料は以下の通りである。
C.I. Pigment Yellow 185：BASF社製「パリオトールエローＤ１１５５」
C.I. Pigment Yellow 139：BASF社製「パリオトールエローＤ１８１９」
C.I. Pigment Green ７ ：東洋インキ製造株式会社製「LIONOL GREEN YS」

* 1: The pigments used in Examples and Comparative Examples are as follows.
CI Pigment Yellow 185: “Pariotor Yellow D1155” manufactured by BASF
CI Pigment Yellow 139: “Paliotorero D1819” manufactured by BASF
CI Pigment Green 7: “LIONOL GREEN YS” manufactured by Toyo Ink Manufacturing Co., Ltd.

Dye derivative (C)

Dye derivative (D)

Dye derivative (E)

The viscosity of the alkali development type colored resist material obtained in Examples 1 to 8 and Comparative Examples 1 to 3 was adjusted to the viscosity of the next day of adjustment and the viscosity after standing at 40 ° C. for 7 days. "R110"). Storage stability was evaluated with the rate of change in viscosity before and after standing at 40 ° C for 7 days being less than 10%, 10% to less than 20%, 20% to less than 50%, △, 50% to x. did.
Next, the alkali developing type colored resist materials obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at 500 rpm, 1000 rpm, and 1500 rpm. Coating was performed at the number of rotations to obtain three types of coated substrates having different color resist film thicknesses. The resist-coated substrate is dried at 70 ° C. for 20 minutes, exposed to ultraviolet light at an integrated light quantity of 200 mj / cm ² using an ultrahigh pressure mercury lamp, heated at 230 ° C. for 40 minutes, allowed to cool, and then subjected to a contrast ratio by the following method. Was measured. The evaluation results are shown in Table 2.

<Measurement method of contrast ratio>
A resist-coated substrate is sandwiched between two polarizing plates, and the transmitted light when the two polarizing plates are parallel is measured with a luminance meter to obtain parallel luminance, and the transmitted light when the two polarizing plates are orthogonal to each other. The contrast ratio was calculated from the following formula as orthogonal luminance measured with a meter.
Contrast ratio = parallel luminance / orthogonal luminance In addition, a color luminance meter ("BM-5A" manufactured by Topcon Corporation) is used as the luminance meter, and a commercially available polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) is used as the polarizing plate. )). In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

表２から明らかなように、本発明の着色組成物は、分散安定性、保存安定性に優れ、かつ本発明の着色組成物を用いて形成された塗膜は、コントラスト比が高い。
また、本発明の着色組成物を用いてフィルタセグメントを形成することにより、色むらがなく、コントラスト比が高く、高精細なカラーフィルタを得ることができた。

As is apparent from Table 2, the colored composition of the present invention is excellent in dispersion stability and storage stability, and the coating film formed using the colored composition of the present invention has a high contrast ratio.
Moreover, by forming a filter segment using the colored composition of the present invention, a high-definition color filter having no color unevenness and a high contrast ratio could be obtained.

Claims (5)

A coloring composition for a color filter, comprising at least a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, an organic pigment, and a compound represented by the following general formula (1).

(In the formula, X represents O or NH. R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alicyclic group which may have a group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and a substituent Aryloxy group which may have a substituent, alkylthio group which may have a substituent, arylthio group which may have a substituent, alkylamino group which may have a substituent, dialkyl which may have a substituent An amino group, an arylamino group which may have a substituent, a diarylamino group which may have a substituent, a halogen atom, a nitro group, a sulfonic acid group, a carboxyl group, a formyl group, or a substituent A good phthalimidomethyl group or an optionally substituted substituent It represents a Hon'amido group.)   The coloring composition for a color filter according to claim 1, wherein the organic pigment is an isoindoline pigment.   The coloring composition for a color filter according to claim 2, wherein the isoindoline pigment is C.I. Pigment Yellow 185 pigment.   The color filter according to any one of claims 1 to 3, wherein the content of the compound represented by the general formula (1) is 5 to 20 parts by weight with respect to 100 parts by weight of the organic pigment. Coloring composition. A color filter comprising a filter segment formed from the colored composition according to claim 1.