JP2003240938A - Coloring composition for color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition capable of forming a color filter having excellent color characteristics, especially having high transmittance and thereby having high luminosity and to provide the color filter having satisfactory color characteristics. <P>SOLUTION: The coloring composition for the color filter comprises a coloring agent carrier consisting of a transparent resin, a precursor thereof or the mixture thereof and a specified azo pigment represented by C.I.Pigment Yellow 214 and dispersed in the coloring agent carrier. The color filter comprises a YMC color filter wherein at least one yellow color filter segment is formed by using the coloring composition and an RGB color filter wherein at least one red color or green color filter segment is formed by using the coloring composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 is one in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It consists of things arranged in a fixed array. The filter segments are as fine as several microns to several hundreds of microns, and are arranged in a predetermined arrangement for each hue. A transparent electrode for driving the liquid crystal is generally formed by vapor deposition or sputtering on the color filter used in the color liquid crystal display device, and an alignment film for orienting the liquid crystal in a certain direction is further formed on the transparent electrode. Has been done. In order to sufficiently obtain the performance of these transparent electrode and alignment film, it is necessary to perform the forming step at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

Therefore, at present, as a method of manufacturing a color filter, a method called a pigment dispersion method, which uses a pigment having excellent light resistance and heat resistance as a colorant, is mainly used, and the following two methods are mainly used. Color filters are manufactured in. In the first method, a photosensitive transparent resin solution in which a pigment is dispersed is applied to a transparent substrate such as glass, the solvent is removed by drying, and then pattern exposure of one filter color is performed, and then the unexposed portion is exposed. Is removed in the developing step to form a pattern of the first color, and after treatment such as heating is added as necessary,
A color filter can be manufactured by sequentially repeating the same operation for all filter colors.

In the second method, a transparent resin solution in which a pigment is dispersed is applied to a transparent substrate such as glass, the solvent is removed by drying, and then a resist such as a positive resist is applied on the coating film. Then, pattern exposure of one filter color is performed, development is performed to form a resist pattern, and this is used as an etching resist to remove the pigment-dispersed coating film on which the resist pattern is not adhered with an etching solution and peel off the resist coating film. Then, a color filter can be manufactured by forming a pattern for the first color, adding a treatment such as heating if necessary, and then repeating the same operation sequentially for all filter colors. The development of the resist and the etching of the pigment-dispersed coating film can be performed simultaneously.

[0005]

In the above method, a coloring composition containing a yellow pigment is used for producing a yellow, red or green filter segment, and conventionally CI Pigment Yellow 139 has been used as the yellow pigment.
However, under the circumstances where the color characteristics of the color filter such as the transmittance, that is, the improvement of the lightness and the color purity, the coating uniformity when forming pixels, the sensitivity, the developability, and the pattern shape are increasing, CI adopted by
Pigment Yellow 139 has become difficult to handle. In recent years, in particular, liquid crystal display devices have been applied to television monitors, and bright color filters have been demanded for producing low power consumption panels.

Therefore, an object of the present invention is to provide excellent color characteristics,
It is an object of the present invention to provide a coloring composition which can form a color filter having particularly high transmittance and therefore high brightness. Another object of the present invention is to provide a color filter having good color characteristics.

[0007]

The inventors of the present invention can control the spectral spectrum of a filter segment by using a coloring composition for a color filter containing a specific azo-based pigment as a yellow pigment, and have high brightness and high color. The present invention has been completed by finding that a color filter having a high degree of purity can be obtained.

That is, the present invention comprises a colorant carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and an azo pigment represented by the following general formula (1) dispersed in the colorant carrier. There is provided a coloring composition for a color filter, comprising: General formula (1)

[Chemical 2] [In the formula, R ₁ and R ₂ are each independently H, C
_{H 3, OCH 3, OC 2} H 5, Cl, Br, NO 2, or an COOCH _2. ]

The coloring composition of the present invention preferably contains a pigment derivative having a basic group or a triazine derivative having a basic group. Further, the content of the pigment derivative having a basic group or the triazine derivative having a basic group is preferably 0.001 to 40% by weight based on the azo pigment represented by the general formula (1).

The invention also comprises at least one cyan color filter segment, at least one magenta color filter segment and at least one yellow color filter segment, the at least one yellow color filter segment of the invention. Provided is a color filter formed of a coloring composition. Furthermore, the present invention comprises at least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one red filter segment or green filter segment is a colored composition of the invention. And a color filter formed of

The azo pigment represented by the above general formula (1) (hereinafter referred to as the azo pigment of the present invention) is CI Pigme.
The contrast is higher than that of nt Yellow 139, and not only when using a coloring composition in which the pigment is dispersed alone in a colorant carrier, but also when using a coloring composition in which the pigment is mixed with another pigment and dispersed. Can also form filter segments with high contrast. Further, in the yellow color filter segment formed from the coloring composition of the present invention in which the azo pigment of the present invention is dispersed in a colorant carrier, the transmission wavelength region is shifted to the short wavelength side, and the transmission region is widened to increase the transmittance. Becomes higher.

Specifically as the azo pigment of the present invention, CI Pigment Yellow 214 is represented by a color index number.
In addition to (Compound (1) shown in Table 1 below), pigments shown in Tables 1 to 6 below can be given, but the pigments are not limited to these. Above all, in the above general formula (1), R
_An azo pigment in which ₁ is H and R ₂ is CH ₃ is preferable because it is excellent in hue and solvent resistance.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

[0016]

[Table 4]

[0017]

[Table 5]

[0018]

[Table 6]

The colorant carrier in which the azo pigment of the present invention is dispersed is composed of a transparent resin, a precursor thereof or a mixture thereof as described above. 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 the precursor thereof includes a monomer or an oligomer that is cured by irradiation with radiation to generate a transparent resin. Two or more kinds can be mixed and used. A photoinitiator or the like is added to the colored composition for a color filter of the present invention when the composition is cured by irradiation with ultraviolet rays.

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. , Phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, celluloses, polybutadiene, polyimide resin and the like. Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin and urea resin.

As the photosensitive resin, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group, and a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group, an epoxy group or the like. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is treated with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product can also be used.

The monomers and oligomers are 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth)
Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate,
Various acrylic and methacrylic acid esters such as melamine (meth) acrylate and epoxy (meth) acrylate, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile, etc. Can be mentioned.

As the photoinitiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -butan-1-one and other acetophenone-based photoinitiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-based photoinitiators such as benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, Benzophenone-based photoinitiators such as methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenylsulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, Thioxanthone photoinitiators such as isopropylthioxanthone and 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (Trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl)- s-triazine, 2-pipenyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-
1-yl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (4-methoxy-naphth-1-yl)
-4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-
Triazine-based photoinitiators such as triazine and 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate-based photoinitiators, carbazole-based photoinitiators, and imidazole-based photoinitiators are used.

The above photoinitiators may be used alone or in admixture of two or more, and as the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthene is used. Lenquinone, camphorquinone, ethylanthraquinone,
4,4'-diethylisophthalophenone, 3,3 ',
4,4'-Tetra (t-butylperoxycarbonyl)
Compounds such as benzophenone and 4,4′-diethylaminobenzophenone can also be used in combination.

The coloring composition for color filters of the present invention comprises
After mixing the azo pigment with other pigments as needed, the resulting pigment composition, together with the photoinitiator as needed, in a colorant carrier, three-roll mill, two-roll mill, sand mill It can be finely dispersed and manufactured using various dispersing means such as a kneader. Further, the coloring composition for a color filter of the present invention can also be produced by mixing the azo pigment and the other pigment separately dispersed in a colorant carrier.

When the pigment is dispersed in the colorant carrier, a dispersion aid such as a resin type pigment dispersant, a surfactant or a dye derivative can be appropriately contained. Since the dispersion aid is excellent in dispersing the pigment and has a large effect of preventing re-aggregation of the pigment after dispersion, when a coloring composition obtained by dispersing the pigment in the colorant carrier using the dispersion aid is used. Provides a color filter with excellent transparency.

The resin-type pigment dispersant has a pigment-affinity portion having a property of adsorbing to the pigment and a portion having compatibility with the colorant carrier, and is adsorbed to the pigment to disperse the pigment in the colorant carrier. It serves to stabilize the. Specific examples of the resin type pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, and the like Salt or the like is used. Further, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid-
(Meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins and water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, A phosphoric acid ester or the like is used. These may be used alone or in admixture of two or more.

As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, alkyl diphenyl ether. Sodium disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether Anionic surfactants such as phosphate ester; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polio Shi nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate,
Nonionic surfactants such as polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkylbetaines such as betaine alkyldimethylaminoacetate and alkylimidazolines. The agents may be mentioned, and these may be used alone or in admixture of two or more.

The dye derivative is a compound in which a substituent is introduced into an organic dye. Organic dyes also include pale yellow aromatic polycyclic compounds such as naphthalene-based and anthraquinone-based compounds which are not generally called dyes. Examples of the dye derivative include JP-A-63-305173 and JP-B-57-1562.
No. 0, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63
Those described in Japanese Patent Publication No. -17102, Japanese Patent Publication No. 5-9469, etc. can be used alone or in combination.
A mixture of more than one type can be used. In particular, the pigment derivative having a basic group or the triazine derivative having a basic group has a large effect of dispersing the pigment, and thus is preferably used.

Specific examples of the basic group of the dye derivative include the following general formulas (2), (3), (4) and (5).
And a substituent represented by. General formula (2)

[Chemical 3] General formula (3)

[Chemical 4] General formula (4)

[Chemical 5] General formula (5)

[Chemical 6]

[Wherein X: --SO _2- , --CO--, --C
H ₂ NHCOCH ₂ -, - represents a or a direct bond - CH _2. n represents an integer of 1 to 10. R ₁ and R ₂ : each independently, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a combination of R ₁ and R ₂ It represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom. R ₃ represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. R ₄ , R ₅ , R ₆ , and R ₇ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. _{Y: -NR 8 -Z-NR 9} - or a direct bond. R ₈ and R ₉ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. Z: represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted phenylene group. P: Substituent represented by general formula (6) or general formula (7)
Represents a substituent represented by. Q: represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (6) or a substituent represented by the general formula (7).

General formula (6)

[Chemical 7] General formula (7)

[Chemical 8]

Examples of the organic dye constituting the pigment derivative having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine and flavan. Anthraquinone dyes such as thoron, antoanthrone, indanthrone, pyrantrone and violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes Examples thereof include dyes, slene dyes, and metal complex dyes. Further, it may be a pigment used in a color filter coloring composition described later.

The triazine constituting the triazine derivative having a basic group includes an alkyl group such as a methyl group and an ethyl group, an amino group or an alkylamino group such as a dimethylamino group, a diethylamino group and a dibutylamino group, a nitro group, Hydroxyl group or methoxy group, ethoxy group, alkoxy group such as butoxy group, halogen such as chlorine or methyl group, methoxy group, amino group, dimethylamino group, phenyl group or methyl group which may be substituted with hydroxyl group,
1,3,5 which may have a substituent such as a phenylamino group which may be substituted with an ethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, a diethylamino group, a nitro group or a hydroxyl group. -Triazine.

The pigment derivative having a basic group of the present invention is
It can be synthesized by various synthetic routes. For example, after introducing the substituents represented by the following formulas (8) to (11) into the organic dye, it reacts with the substituents to form the substituents represented by the general formulas (2) to (5). Amine components such as N, N
-Dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6-
[3- (dibutylamino) propylamino] -1,3
It is obtained by reacting 5-triazin-2-ylamino] aniline and the like.

Formula (8) --SO ₂ Cl Formula (9) --COCl Formula (10) --CH ₂ NHCOCH ₂ Cl Formula (11) --CH ₂ Cl

When the organic dye is an azo dye, the substituents represented by the general formulas (2) to (5) are introduced into the diazo component or the coupling component in advance, and then the coupling reaction is carried out to form a base. It is also possible to produce an azo pigment derivative having a functional group. Further, the triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component forming a substituent represented by the general formulas (2) to (5) in at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N -Methylpiperazine or the like, and then obtained by reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

Examples of the amine component used to form the substituents represented by formulas (2) to (7) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N- Ethylpropylamine,
N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-te
rt-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexyl Amine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, 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-dibutyl Aminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine,
N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, Three
-Piperidine methanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidine ethanol, 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.

As the dye derivative, those shown in Tables 7 to 15 can be used, but the dye derivative is not limited thereto. The dye derivative can be used alone or in combination of two or more.

[0040]

[Table 7]

[0041]

[Table 8]

[0042]

[Table 9]

[0043]

[Table 10]

[0044]

[Table 11]

[0045]

[Table 12]

[0046]

[Table 13]

[0047]

[Table 14]

[0048]

[Table 15]

The coloring composition of the present invention may contain other organic or inorganic colorants in addition to the azo pigment of the present invention, depending on the hue of the filter segment to be formed. Examples of the organic colorant include dyes, organic pigments and natural pigments, and examples of the inorganic colorant include inorganic pigments. The inorganic pigment includes an extender pigment. As the colorant, a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance is preferable,
Organic colorants are usually used, and organic pigments are particularly preferred. The organic or inorganic colorants may be used alone or in combination of two or more. Specific examples of organic pigments that can be used in the coloring composition of the present invention are shown below by color index numbers.

When a yellow color filter segment is formed from the coloring composition of the present invention, CI Pigment Yello
w 1, 2, 3, 4, 5, 6, 10, 12, 13, 14,
15, 16, 17, 18, 24, 31, 32, 34, 3
5, 35: 1, 36, 36: 1, 37, 37: 1, 4
0, 42, 43, 53, 55, 60, 61, 62, 6
3, 65, 73, 74, 77, 81, 83, 93, 9
4, 95, 97, 98, 100, 101, 104, 10
6, 108, 109, 110, 113, 114, 11
5, 116, 117, 118, 119, 120, 12
3, 126, 127, 128, 129, 138, 13
9, 147, 150, 151, 152, 153, 15
4, 155, 156, 161, 162, 164, 16
6, 167, 168, 169, 170, 171, 17
2,173,174,175,176,177,17
9, 180, 181, 182, 185, 187, 18
Yellow pigments such as 8, 193, 194, 199, 198 and 213 can be used in combination. In this case, the content of the azo pigment of the present invention based on the total amount of the colorant (the total amount of the azo pigment of the present invention and the other yellow pigment) is different depending on the required color characteristics, but is sufficient. From the viewpoint of obtaining high brightness, it is preferably 10% by weight or more. Further, when particularly high brightness is required, it is preferable to use only the azo pigment of the present invention without using other yellow pigments in combination.

When a red filter segment is formed from the coloring composition of the present invention, CI Pigment Red 7, 1 is used.
4, 41, 48: 1, 48: 2, 48: 3, 48: 4,
81: 1, 81: 2, 81: 3, 146, 177, 17
8, 184, 185, 187, 200, 202, 20
8, 210, 246, 254, 255, 264, 27
Red pigments such as 0, 272 are used together. In this case, the content of the azo pigment of the present invention based on the total amount of the colorant (the total amount of the azo pigment of the present invention and the red pigment) is 0.01 to 4
It is preferably 0% by weight, particularly preferably 1 to 30% by weight. When the content of the azo pigment of the present invention is less than 0.01% by weight, the lightness is low, and when it exceeds 40% by weight, it is close to yellowish (orange) and the hue is not good. Further, a part of the azo pigment of the present invention can be replaced with the above-mentioned other yellow pigment.

When a green filter segment is formed from the coloring composition of the present invention, CI Pigment Green 7,
Green pigments such as 10, 36 and 37 are used together. in this case,
The content of the azo pigment of the present invention based on the total amount of the colorant (the total amount of the azo pigment of the present invention and the green pigment) is 0.
It is preferably from 01 to 90% by weight, particularly preferably from 10 to 50% by weight. When the content of the azo pigment of the present invention is less than 0.01% by weight, it is too blue and the lightness becomes low, and when it exceeds 90% by weight, it shifts to yellow green and the hue is not good. Further, a part of the azo pigment of the present invention can be replaced with the above-mentioned other yellow pigment.

The coloring composition of the present invention contains titanium oxide, barium sulfate, zinc white, in order to secure good coatability, sensitivity, developability and the like while balancing the saturation and lightness.
Lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (II
I)), cadmium red, ultramarine blue, navy blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be contained.

When the coloring composition of the present invention contains two or more kinds of coloring agents, the coloring composition of the present invention requires the obtained coloring agent mixture after mixing two or more kinds of coloring agents. According to the above, it can be produced by finely dispersing it in a colorant carrier by a known method together with the above-mentioned photoinitiator. Further, the coloring composition of the present invention can also be produced by mixing each colorant separately finely dispersed in a colorant carrier.

Further, in the coloring composition of the present invention, the coloring agent is sufficiently dispersed in the coloring agent carrier and applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate the formation of the filter segment with a solvent. 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, methyl ethyl ketone. , Ethyl acetate, methanol,
Examples include ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum-based solvents, and the like, which may be used alone or in combination.

The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include organic acids such as benzyl trimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, lactic acid, oxalic acid and its methyl ether, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples include phosphine and phosphite.

The coloring composition of the present invention can be prepared in the form of an ink jet ink, a gravure offset printing ink, a waterless offset printing ink, a silk screen printing ink, a solvent developing type or an alkali developing type colored resist material. . The colored resist material is a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, and a photoinitiator, and the azo pigment of the present invention and, if necessary, other colorants dispersed therein. Is.

When the filter segment is formed by the photolithographic method, the azo pigment of the present invention and other coloring agents used as necessary are added in a total amount of 1.5 to 7% by weight in the coloring composition. It is preferable to contain it in a ratio of. Further, when the filter segment is formed by the printing method, it is preferable that the total amount of the filter segment is contained in the coloring composition in an amount of 1.5 to 40% by weight. In any case,
The colorant is preferably 10 in the final filter segment.
-40% by weight, more preferably 20-40% by weight, with the balance consisting essentially of the resinous binder provided by the colorant carrier.

The colored composition of the present invention can be coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more, by means of centrifugation, sintering filter, membrane filter or the like. And it is preferable to remove the mixed dust.

As mentioned above, the color filter of the invention comprises at least one red filter segment, at least one blue filter segment, at least one green filter segment, wherein at least one red filter segment or green. The filter segment is formed using the coloring composition of the present invention. The blue filter segment can be formed by using an ordinary blue coloring composition. Instead of the azo pigment of the present invention, a blue coloring composition can be obtained, for example, by CI PigmentBlue 1
5, 15: 1, 15: 2, 15: 3, 15: 4, 15:
It is a composition obtained by using blue pigments such as 6, 16, and 60. CI Pigment Violet 1, 1 for blue composition
Purple pigments such as 9, 23, 27, 32 and 42 can be used in combination.

The color filter of the present invention also comprises at least one magenta color filter segment, at least one cyan color filter segment, at least one yellow color filter segment, wherein at least one yellow color filter segment is Formed using the coloring composition of the present invention. The magenta color filter segment can be formed using a conventional magenta coloring composition. The magenta coloring composition is, for example, CI Pigment Violet instead of the azo pigment of the present invention.
1, 19, CI Pigment Red 144, 146, 17
It is a composition obtained by using pigments such as 7, 169 and 181. The cyan color filter segment can be formed by using an ordinary cyan color composition. Cyan color coloring composition, instead of the azo pigment of the present invention, for example C.
I. Pigment Blue 15: 1, 15: 2, 15: 4, 1
It is a composition obtained by using pigments such as 5: 3, 15: 6, 16, and 60.

The color filter of the present invention can be manufactured by forming a filter segment of each color on a transparent substrate using the coloring composition of the present invention by a printing method or a photolithography method. As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate is used.

The formation of each color filter segment by the printing method can be patterned by simply printing and drying the coloring composition prepared as each of the above-mentioned various printing inks. It has excellent properties. Further, the development of printing technology enables printing of fine patterns having high dimensional accuracy and smoothness. To print, on the printing plate,
Alternatively, the composition is preferably such that the ink does not dry and solidify on the blanket. In addition, it is important to control the fluidity of the ink on the printing machine, and it is possible to adjust the ink viscosity with a dispersant or an extender pigment.

When each color filter segment is formed by the photolithography method, the coloring composition prepared as the solvent developing type or alkali developing type colored resist material is spray-coated, spin-coated, slit-coated, or roll-coated on a transparent substrate. It is applied by a coating method such as a coat so that the dry film thickness is 0.2 to 5 μm.
If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern which is provided in contact or non-contact with the film. Then, after immersing in a solvent or an alkaline developing solution or spraying a developing solution 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 carried out as necessary. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above printing method.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. Incidentally, in order to increase the ultraviolet exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin,
For example, it is also possible to apply polyvinyl alcohol, a water-soluble acrylic resin, or the like and dry it to form a film that prevents polymerization inhibition by oxygen, and then perform UV exposure.

The color filter of the present invention can be manufactured by an electrodeposition method, a transfer method or the like in addition to the above method.
The coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by utilizing a transparent conductive film formed on a transparent substrate and by electrophoresing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is previously formed on the surface of a peelable transfer base sheet and the color filter layer is transferred to a desired transparent substrate.

[0067]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “part” means “part by weight”. First, the preparation of the acrylic resin solutions used in Examples and Comparative Examples will be described.

(Preparation of Acrylic Resin Solution) 450 parts of cyclohexanone were placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and the mixture of the following monomer and thermal polymerization initiator was added at the same temperature for 1 hour. Was added dropwise to carry out a polymerization reaction. Methacrylic acid 20.0 parts Methyl methacrylate 10.0 parts Butyl methacrylate 55.0 parts Hydroxyethyl methacrylate 15.0 parts Azobisisobutyronitrile 4.0 parts After dropping, and further reacting at 80 ° C. for 3 hours, azobis A solution prepared by dissolving 1.0 part of isobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 80 ° C. for 1 hour to obtain a solution of an acrylic resin having a weight average molecular weight of about 40,000. 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 resin solution synthesized above so that the nonvolatile content became 20% by weight. To prepare an acrylic resin solution.

Example 1 A mixture having the following composition was uniformly stirred and mixed, and then glass beads having a diameter of 1 mm were used.
After being dispersed in a sand mill for 5 hours, it was filtered through a 5 μm filter to prepare an azo yellow pigment dispersion. Azo yellow pigment CI Pigment Yellow 214 9.0 parts ("PV FAST YELLOW H9G" manufactured by Clariant) Dye derivative (Compound A-45) 1.0 part Acrylic resin solution 50.0 parts Cyclohexanone 40.0 parts The mixture having the composition was stirred and mixed so as to be uniform, and then filtered with a 1 μm filter to obtain an alkali developing yellow resist material. Azo yellow pigment dispersion 60.0 parts Acrylic resin solution 11.0 parts Trimethylol propane triacrylate 4.2 parts (Shin Nakamura Chemical Co., Ltd. "NK ester ATMPT") Photoinitiator (Ciba Geigy Co. "Irgacure 907" ) 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Cyclohexanone 23.2 parts

[Comparative Example 1] An azo yellow pigment was replaced with an isoindoline yellow pigment CI Pigment Yellow 139 (BASF
An alkali development type yellow resist material was produced in the same manner as in Example 1 except that the product was changed to "Paliotor Yellow D1819".

The resist materials obtained in Example 1 and Comparative Example 1 were placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm at 500 rpm using a spin coater and 1 rpm.
The coating was performed at the rotation speeds of 000 rpm, 1500 rpm, and 2000 rpm to obtain four types of coated substrates having different film thicknesses. Next, after drying at 70 ° C. for 20 minutes, ultraviolet exposure was performed using an ultrahigh pressure mercury lamp with an integrated light amount of 150 mJ. After heating the coated substrate at 230 ° C. for 1 hour and allowing it to cool, the chromaticity (Y, x, y) of the obtained yellow coating film at the C light source is measured by a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Was measured using. 400-70 from 4 sets of chromaticity / spectroscopy results
The maximum transmittance (Tmax), x, y, and Y when the minimum value (Tmin) of the spectral transmittance at 0 nm wavelength was 1% were obtained. Furthermore, the surface state of the coated substrate at 1000 rpm was observed with an optical microscope (“BX60” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 16.

[0072]

[Table 16]

As shown in Table 16, the yellow coating film formed using the resist material of Comparative Example 1 had a brightness Y of 76.67.
On the other hand, the yellow coating film formed using the resist material of Example 1 has a large brightness Y of 92.85, and the yellow coating film formed using the coloring composition (resist material) of the present invention. Membranes are much better. Further, x is small for the same y, and the color purity is improved.

[Example 2] 5.1 parts of an azo yellow pigment was used as a copper phthalocyanine green pigment CI Pigment Green 36 (Toyo Ink Mfg. Co., Ltd. "Rionol Green 6YK") 5.1
75 parts and azo yellow pigment CI Pigment Yellow 214
("Clearant" PV FAST YELLOW
H9G ") An alkaline developing green resist material was obtained in the same manner as in Example 1 except that the amount was changed to 3.825 parts.

[Comparative Example 2] 5.175 parts of copper phthalocyanine green pigment was changed to 7.6 parts, and azo yellow pigment 3.2 was used.
85 parts of isoindoline yellow pigment CI Pigment Yello
w 139 (BASF Corporation "Pariotor Yellow D181
9 ") An alkaline developing green resist material was obtained in the same manner as in Example 2 except that the amount was changed to 1.4 parts.

The resist material obtained in Example 2 and Comparative Example 2 was placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.3 mm by using a spin coater, and x = 0.32, y.
It was applied to a film thickness of 0.53. Next, 70 ℃
After being dried for 20 minutes at 80 ° C., it was exposed to ultraviolet rays with an integrated light amount of 150 mJ using an ultra-high pressure mercury lamp. Coating substrate at 230 ℃
After heating for 1 hour at room temperature and allowing to cool, a microscopic spectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) was used to obtain the brightness (Y) at the C light source of the green coating film and the maximum transmittance (Tma
x) and the minimum transmittance (Tmin) were determined. Furthermore, the surface condition of the coating film is observed with an optical microscope ("BX60" manufactured by Olympus Optical Co., Ltd.).
Observed at. The results are shown in Table 17.

[0077]

[Table 17] As shown in Table 17, the green coating film formed by using the coloring composition (resist material) of the present invention had a brightness Y even when x and y (hue) were adjusted by using a yellow pigment in combination.
Is high and excellent.

Example 3 In order to produce a color filter having a red filter segment, a blue filter segment and a green filter segment, blue and red resist materials were produced by the following method.

(Blue Resist Material) A mixture having the following composition was uniformly stirred and mixed, and then dispersed with a glass mill having a diameter of 1 mm in a sand mill for 5 hours and then filtered through a filter of 5 μm to prepare a copper phthalocyanine dispersion. did. ε-type copper phthalocyanine pigment CI Pigment Blue 15: 6 10.0 parts (BASF product “Heliogen Blue L-6700F”) Dispersant (Zeneca product “Solvers 20000”) 2.0 parts Acrylic resin solution 40.0 parts Cyclohexanone Next, 48.0 parts of the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a 1 μm filter to obtain a blue resist material. Copper phthalocyanine dispersion 60.0 parts Acrylic resin solution 11.0 parts Trimethylolpropane triacrylate 4.2 parts (Shin Nakamura Chemical Co., Ltd. “NK ester ATMPT”) Photoinitiator (Ciba Geigy “Irgacure 907”) 1 .2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Cyclohexanone 23.2 parts

(Red resist material) 10.0 parts of ε-type copper phthalocyanine pigment was used as a diketopyrrolopyrrole red pigment CI.
Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Geigy), 8.33 parts, azo red pigment CI P
igment Red 177 (“Chromophtal Red A2B” manufactured by Ciba-Geigy) and azo yellow pigment CI
Pigment Yellow 214 ("Clearant" PV FAS
T YELLOW H9G ") A red resist material was prepared in the same manner as the blue resist material except that the content was changed to 0.34 part.

A red resist material was applied onto a glass substrate by spin coating so as to have a film thickness of chromaticity (x, y) shown in Table 18. After drying, a striped pattern exposure is carried out with an exposure machine and developed with an alkali developing solution for 90 seconds,
Striped red filter segments were formed.
The alkaline developer is sodium carbonate 1.5% by weight.
0.5% by weight of sodium hydrogen carbonate 8.0% by weight of an anionic surfactant ("Perirex NBL" manufactured by Kao Corporation) and 90% by weight of water.

Then, in the same manner as the red resist material, the green resist material obtained in Example 2 was tested for chromaticity (x,
It was applied so as to have the film thickness of y). After drying, pattern exposure in a stripe shape adjacent to the red filter segment was performed using an exposure machine to form a stripe-shaped green filter segment. Furthermore, similar to the red resist material,
A blue resist material was applied so as to have a film thickness of chromaticity (x, y) shown in Table 18 to form striped blue filter segments adjacent to the red and green filter segments. The shape of each color filter segment is good,
The resolution was also good. Finally, the obtained color filter is heated in an oven at 230 ° C. for 30 minutes to completely react the remaining polymerizable functional group, and a red, green, and blue stripe-shaped stripes are formed on the transparent substrate. A color filter with filter segments was obtained.

[Comparative Example 3] An azo yellow pigment was used as CI Pigme.
nt Yellow 139 (Basio's "Pariotor Yellow D
1819 "), but a red resist material was produced in the same manner as in Example 3. Using the obtained red resist material, the green resist material manufactured in Comparative Example 2, and the blue resist material manufactured in Example 3, a color filter was manufactured in the same manner as in Example 3.

The Y of each color of the color filters obtained in Example 3 and Comparative Example 3 was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Also,
White light is obtained when light is transmitted through all three colors.
The x, y, Y of the white light was calculated from the x, y, Y of each color. The results are shown in Tables 14 and 15. As shown in Table 15, the Y value of the color filter obtained in Example 3 is higher than that obtained in the comparative example. When the Y value is high, the color filter has a bright white color.

[0085]

[Table 18]

[Table 19]

Example 4 To prepare a color filter having a cyan color filter segment, a magenta color filter segment, and a yellow color filter segment, a cyan color and magenta color resist material was manufactured by the following method. (Cyan color resist material) ε type copper phthalocyanine pigment β
Type Copper Phthalocyanine Pigment CI Pigment Blue 16 (BAS
A cyan resist material was produced in the same manner as the blue resist material of Example 3 except that the product was changed to "Heliogen Blue D-7565" manufactured by F.

(Magenta color resist material) ε-type copper phthalocyanine pigment is a quinacridone red pigment CI Pigment Red
122 (Chosta Geigy's "Hosta Palm Pink E")
A magenta resist material was prepared in the same manner as the blue resist material of Example 3 except that the above was changed to. The obtained cyan color resist material, magenta color resist material, and yellow color resist material obtained in Example 1 were treated in the same manner as in Example 3 to obtain the chromaticity (x, y) film thicknesses shown in Table 20. So that the cyan, magenta, and yellow colors are applied on the transparent substrate.
A color filter having stripe-shaped filter segments of three colors was obtained.

Comparative Example 4 The cyan resist material and magenta resist material obtained in Example 4 and the yellow resist material obtained in Comparative Example 1 are shown in Table 20 in the same manner as in Example 3. It is applied so that the film thickness has the chromaticity (x, y) shown, and cyan, magenta, and yellow colors are applied on the transparent substrate.
A color filter having stripe-shaped filter segments of three colors was obtained.

The Y of each color of the color filters obtained in Example 4 and Comparative Example 4 was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co.). White light is obtained when light is transmitted through all three colors, and x, y, Y of the white light is calculated from x, y, Y of each color. The results are shown in Tables 20 and 21. As shown in Table 21, the Y value of the color filter obtained in Example 4 is higher than that obtained in Comparative Example 4. When the Y value is high, the color filter has a bright white color.

[0090]

[Table 20]

[Table 21]

[0091]

The colored composition of the present invention has a transmission wavelength region shifted to the short wavelength side, and thus a green, yellow or red filter segment having extremely high brightness can be formed on a substrate. A color filter comprising a filter segment formed by using the coloring composition of the present invention is capable of simultaneously imparting high brightness and high saturation to a color liquid crystal display device, and a transmissive / reflective color liquid crystal display device and It is suitable as a color filter for color separation of a solid-state image sensor.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C09B 33/153 C09B 33/153 F term (reference) 2H048 BA02 BA47 BA57 BB02 BB42 BB46 2H091 FA02Y FB02 FB12 4J002 AA001 AA011 AA021 AB011 AC001 BB181 BB241 BC031 BC071 BD031 BD051 BF021 BG001 BG041 BH021 BL011 CC031 CC161 CC181 CD001 CF001 CF011 CK021 CL001 CM041 CM051 EQ016 EU027 EU037 EU107 EU187 EU9603FD97 FD GP0

Claims (5)

[Claims] 1. A colorant carrier comprising a transparent resin, a precursor thereof or a mixture thereof, and an azo pigment represented by the following general formula (1) dispersed in the colorant carrier. Coloring composition for color filter. General formula (1) [In the formula, R ₁ and R ₂ are each independently H, C
_{H 3, OCH 3, OC 2} H 5, Cl, Br, NO 2, or an COOCH _2. ] 2. The coloring composition according to claim 1, comprising a pigment derivative having a basic group or a triazine derivative having a basic group. 3. The content of the pigment derivative having a basic group or the triazine derivative having a basic group is represented by the general formula (1).
The coloring composition according to claim 2, which is contained in an amount of 0.001 to 40% by weight based on the azo pigment represented by. 4. At least one cyan filter segment, at least one magenta filter segment, and at least one yellow filter segment, said at least one yellow filter segment according to claim 1. A color filter formed from the coloring composition described. 5. At least one red filter segment, at least one blue filter segment, and at least one green filter segment, wherein the at least one red filter segment or green filter segment is any of claims 1-3. A color filter formed from the coloring composition described.