JP5281738B2 - Coloring composition for color filter and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition for color filters having good developability and high sensitivity and giving an excellent pattern form of formed filter segments, even when a pigment which is made fine is used, and to provide a color filter having filter segments of an excellent pattern form. <P>SOLUTION: The colored composition for color filters contains a pigment carrier comprising a transparent resin and a precursor thereof, a pigment and a photopolymerization initiator having 2-4 hydroxyl groups. The color filter has filter segments formed from the colored composition. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a colored 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.

In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for contrast.
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 vertically and horizontally. It is made up of those arranged in 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.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, 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.
However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

Until now, in order to realize high brightness and high contrast of the color filter, the pigment contained in the filter segment has been refined.
However, when the pigment is made finer, problems such as deterioration in developability occur. In order to solve such problems, it is necessary to improve the developability of the photosensitive coloring composition. Generally, (1) selection of the acid value and molecular weight of the resin, and (2) selection or increase of the monomer. Is done.
JP 2000-72814 A Japanese Patent Laid-Open No. 2004-19979

However, improvement in developability is limited only by increasing the acid value of the resin, decreasing the molecular weight, and selecting or increasing the monomer. In particular, when the amount of monomer is increased, problems such as tackiness occur.
Accordingly, an object of the present invention is to provide a coloring composition for a color filter that has good developability, high sensitivity, and excellent pattern shape of the formed filter segment even when a pigment that has been refined is used. .
Another object of the present invention is to provide a color filter having a filter segment having an excellent pattern shape.

A color filter for coloring composition of the present invention includes a pigment carrier formed of a transparent resin and a precursor thereof, a pigment, a photopolymerization initiator having two hydroxyl groups, a further photoinitiator, 2 The weight ratio of the photopolymerization initiator having a hydroxyl group to the other photopolymerization initiator is 5:95 to 20:80 , and the specific surface area of the pigment is controlled by a grinding method, a precipitation method, or a synthetic precipitation method. It is characterized by being a pigment formed.
Moreover, the color filter of this invention comprises the filter segment formed from the coloring composition of this invention, It is characterized by the above-mentioned.

  Since the coloring composition for a color filter of the present invention uses a photopolymerization initiator having 2 to 4 hydroxyl groups as a photopolymerization initiator, it can be developed even when it contains a fine pigment. Is good, the sensitivity is high, and a filter segment having an excellent pattern shape can be formed.

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 contains a pigment carrier comprising a transparent resin and its precursor, a pigment, and a photopolymerization initiator having 2 to 4 hydroxyl groups.
Examples of the photopolymerization initiator having 2 to 4 hydroxyl groups include 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -[4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methyl-propionyl) -phenoxy] -phenyl} -2-methyl-propan-1-one, 2-hydroxy-1- (4- {2- [4- (2-hydroxy-2-methyl-propionyl) ) -Phenyl] -ethyl} -phenyl) -2-methyl-propan-1-one, 2-hydroxy-1- (4- {1- [4- (2-hydroxy-2-methyl-propionyl) -phenyl] -1,1-dimension Le} - phenyl) -2-methyl - propan-1-one, and the like.

  Among the photoinitiators having 2 to 4 hydroxyl groups, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -[4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one is preferably used from the viewpoint of improving the developing speed.

In the colored composition of the present invention, other photopolymerization initiators can be used together with the photopolymerization initiator.
Other photopolymerization initiators include 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) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone-based photopolymerization initiators such as-[4- (4-morpholinyl) phenyl] -1-butanone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzine Benzoin photopolymerization initiators such as rudimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ' , 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and other benzophenone photopolymerization initiators, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropyl Thioxanthone photopolymerization initiators such as thioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trick (Romethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-) Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, etc. 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Oxime ester photopolymerization initiators such as benzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4, Phosphine photopolymerization initiators such as 6-trimethylbenzoyldiphenylphosphine oxide, quinone photopolymerization initiators such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone, borate photopolymerization initiators, carbazole photopolymerization An initiator, an imidazole photopolymerization initiator, a titanocene photopolymerization initiator, or the like is used. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

  Among the photoinitiators, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl ) Benzophenone, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], Ethanone, 1- [9-ethyl-6- (2- Tilbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide It is preferably used in terms of maintaining sensitivity.

The photopolymerization initiator having 2 to 4 hydroxyl groups and the other photopolymerization initiator are preferably contained in a weight ratio of 1:99 to 60:40, more preferably 5:95 to 50:50. Is done. If the blending amount of the photopolymerization initiator having 2 to 4 hydroxyl groups is less than the above range, the developability is not sufficiently improved. Conversely, if the blending amount is more than the above range, the sensitivity is lowered or formed. The pattern shape of the filter segment may be deteriorated.
The photopolymerization initiator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the pigment in the coloring composition.

  In the coloring composition of the present invention, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 4,4 are used as sensitizers. '-Diethylaminobenzophenone, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) Benzo It may be contained Enon like. The sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

As the pigment, a pigment having a hue of the filter segment to be formed is used.
When forming a red filter segment, the coloring composition of the present invention containing a red pigment is used. As the red pigment, pigments represented by the following general formulas (1) to (3) can be used.

（上記式（１）、（２）において、Ａは、それぞれ独立に、水素原子または置換基を有してもよいアルキル基もしくはアリール基を表す。（３）において、Ｂは、それぞれ独立に、水素原子、置換基を有してもよい飽和もしくは不飽和のアルキル基、シアノ基、置換基を有してもよいアリール基、またはハロゲン基を示す。）
一般式（１）で表される赤色顔料としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １７７が挙げられ、一般式（２）で表される赤色顔料としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ８９が挙げられるが、色相、分光特性の点から、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １７７が好ましい。
一般式（３）で表される赤色顔料としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２５４、２６４等が挙げられるが、色相、分光特性の点から、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２５４が好ましい。

(In the above formulas (1) and (2), A each independently represents a hydrogen atom or an alkyl group or an aryl group which may have a substituent. In (3), each B independently represents A hydrogen atom, a saturated or unsaturated alkyl group which may have a substituent, a cyano group, an aryl group which may have a substituent, or a halogen group.
Examples of the red pigment represented by the general formula (1) include C.I. I. Pigment Red 177, and red pigments represented by the general formula (2) include C.I. I. Pigment Red 89. From the viewpoint of hue and spectral characteristics, C.I. I. Pigment Red 177 is preferred.
Examples of the red pigment represented by the general formula (3) include C.I. I. Pigment Red 254, 264, and the like. From the viewpoint of hue and spectral characteristics, C.I. I. Pigment Red 254 is preferred.

Examples of the red pigment include the red pigments represented by the above general formulas (1) to (3), C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 184, 185, 187, 200, 202, 208, 210, 246, 255, 270, 272, 279, etc. can also be used.
The coloring composition containing a red pigment includes C.I. I. Orange pigments such as Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 can be used in combination.

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

The specific surface area of the red pigment contained in the coloring composition of the present invention is preferably 85 to 130 m ² / g.
When the specific surface area of the red pigment is lower than 85 m ² / g, the luminance and contrast ratio of the color filter are lowered, which is not preferable. In addition, when the specific surface area of the red pigment is higher than 130 m ² / g, it is difficult to maintain stability and fluidity as a colored composition, and the color filter brightness and contrast ratio characteristics are extremely high. Could get worse.

（上記式（４）において、ａは０〜１６の整数を表し、ｂは０〜１６の整数を表し、１４≦ａ＋ｂ≦１６である。） When forming a green filter segment, the coloring composition of the present invention containing a green pigment is used. As the green pigment, a pigment represented by the following general formula (4) can be used.

(In the above formula (4), a represents an integer of 0 to 16, b represents an integer of 0 to 16, and 14 ≦ a + b ≦ 16.)

Examples of the green pigment represented by the general formula (4) include C.I. I. Pigment Green 7, 15, 36, and 37. From the viewpoint of hue and spectral characteristics, C.I. I. Pigment Green 7 and / or C.I. I. Pigment Green 36 is preferred.
Examples of the green pigment include C.I. in addition to the green pigment represented by the general formula (4). I. Green pigments such as Pigment Green 4, 10, 15, 37 can also be used.

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

The specific surface area of the green pigment contained in the colored composition of the present invention is preferably 60 to 100 m ² / g.
When the specific surface area of the green pigment is lower than 60 m ² / g, the luminance and contrast ratio of the color filter are lowered, which is not preferable. In addition, when the specific surface area of the green pigment is higher than 100 m ² / g, it is difficult to maintain stability as a colored composition and ensure fluidity, and the color filter brightness and contrast ratio characteristics are extremely high. Could get worse.

（上記式（５）において、cは0≦c≦1である。） When forming a blue filter segment, the coloring composition of the present invention containing a blue pigment is used. As the blue pigment, a pigment represented by the following general formula (5) can be used.

(In the above formula (5), c is 0 ≦ c ≦ 1.)

Examples of the blue pigment represented by the general formula (5) include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and the like. From the viewpoint of hue and spectral characteristics, C.I. I. Pigment Blue 15: 6 is preferred.
As the blue pigment, in addition to the blue pigment represented by the general formula (5), C.I. I. Blue pigments such as Pigment Blue 16, 22, 60, 64 can also be used.
Examples of the coloring composition containing a blue pigment include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

The specific surface area of the blue pigment contained in the colored composition of the present invention is preferably 90 to 140 m ² / g.
When the specific surface area of the blue pigment is lower than 90 m ² / g, the luminance and contrast ratio of the color filter are lowered, which is not preferable. In addition, when the specific surface area of the blue pigment is higher than 140 m ² / g, it is difficult to maintain stability and fluidity as a colored composition, and the luminance and contrast ratio characteristics of the color filter are extreme. Could get worse.

As a means for controlling the specific surface area of the pigment, a method of controlling the specific surface area by mechanically pulverizing the pigment (referred to as a grinding method), a solution dissolved in a good solvent is introduced into a poor solvent, and a desired specific surface area of the pigment is controlled. There are a method of precipitating a pigment (referred to as a precipitation method), a method of producing a pigment having a desired specific surface area at the time of synthesis (referred to as a synthetic precipitation method), and the like. Depending on the synthesis method and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment.
Each method will be described below, but any of the above methods may be used as a method for controlling the specific surface area of the pigment contained in the colored composition of the present invention.

  In the grinding method, the pigment is mechanically kneaded with a grinding agent such as water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it using a ball mill, sand mill, or kneader (hereinafter, this process is salted). In this method, the inorganic salt and the organic solvent are washed away with water and dried to obtain a pigment having a desired specific surface area. However, since the pigment may crystallize by the salt milling treatment, a method of preventing crystal growth by adding a solid resin or a pigment dispersant that is at least partially dissolved in the organic solvent during the treatment is effective.

As for the ratio of the pigment to the inorganic salt, if the ratio of the inorganic salt is increased, the efficiency of refining the pigment is improved, but the productivity is lowered because the amount of pigment processed is reduced. In general, it is suitable to use 100 to 3000 parts by weight, preferably 200 to 2000 parts by weight of an inorganic salt with respect to 100 parts by weight of the pigment. Further, the water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified, and depending on the blending ratio of the pigment and the inorganic salt, 500 to 3000 weights with respect to 100 parts by weight of the pigment. Part is used.
More specifically, the salt milling is performed by adding a small amount of a water-soluble organic solvent as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, kneading with a kneader or the like, and then pouring the mixture into water. Stir with a speed mixer to make a slurry. Next, this slurry is filtered, washed with water, and dried to obtain a pigment having a desired specific surface area.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired specific surface area. The specific surface area depends on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. The size of can be controlled. In general, pigments are difficult to dissolve in solvents, so the solvents that can be used are limited, but examples include strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, chlorosulfonic acid, or basic solvents such as liquid ammonia, dimethylformamide solution of sodium methylate, etc. It has been known.

  A typical example of this method is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, a method of injecting a sulfuric acid solution into water is generally used from the viewpoint of cost. The sulfuric acid concentration is not particularly limited, but is preferably 95 to 100%. The amount of sulfuric acid used with respect to the pigment is not particularly limited. However, if the amount is too small, the solution viscosity is high and handling becomes bad. Conversely, if the amount is too large, the treatment efficiency of the pigment is lowered. It is preferable. The pigment need not be completely dissolved. The temperature at the time of dissolution is preferably from 0 to 50 ° C. Below this temperature, sulfuric acid may freeze and the solubility will be low. If the temperature is too high, side reactions tend to occur. The temperature of the water to be injected is preferably 1 to 60 ° C., and if the injection is started at a temperature higher than this temperature, it boils with the heat of dissolution of sulfuric acid, and the operation is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 1 part of the pigment. As the time increases, the specific surface area tends to decrease.

The specific surface area of the pigment contained in the coloring composition of the present invention is controlled by selecting a method combining a precipitation method such as an acid pasting method and a grinding method such as a salt milling method, and taking into account the sized particle size of the pigment. However, it is more preferable because the fluidity as a dispersion can be secured at this time.
At the time of salt milling or acid pasting, in order to prevent pigment aggregation associated with the specific surface area control, a dispersion aid such as the following derivatives, resin-type pigment dispersants and surfactants may be used in combination. Further, by controlling the specific surface area in the form of coexisting two or more kinds of pigments, even a pigment that is difficult to disperse alone can be finished as a stable dispersion.

  There is a leuco method as a special precipitation method. When a vat dye, such as a flavantron, perinone, perylene, or indanthrone, is reduced with alkaline hydrosulfite, the quinone group becomes a hydroquinone sodium salt (leuco compound) and becomes water-soluble. A pigment having a large specific surface area that is insoluble in water can be precipitated by adding an appropriate oxidizing agent to the aqueous solution for oxidation.

The synthetic precipitation method is a method of precipitating a pigment having a desired specific surface area simultaneously with the synthesis of the pigment. However, when the produced fine pigment is taken out of the solvent, if the pigment particles are not aggregated into large secondary particles, filtration, which is a general separation method, becomes difficult. It is applied to azo pigments synthesized in water.
Further, as a means for controlling the specific surface area of the pigment, the pigment is dispersed for a long time with a high-speed sand mill or the like (so-called dry milling method in which the pigment is dry-ground in the absence of a grinding aid and an organic liquid). It is also possible to increase the specific surface area and disperse at the same time.

The pigment carrier in which the pigment contained in the colored composition of the present invention is dispersed is composed of a transparent resin and a precursor 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. Transparent resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more.
The transparent resin can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the coloring composition.

  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. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, 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.

  As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or 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 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. 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.

  As monomers and oligomers that are precursors of transparent resins, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) Acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) Various acrylates and methacrylates such as acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( (Meth) acrylamide, N-vinylformamide, acrylonitrile, etc. are mentioned. It can be.

The colored composition of the present invention can be prepared in the form of a solvent development type or alkali development type colored resist. The colored resist is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or an active energy ray curable resin and a monomer, and one or more kinds of pigments are added as necessary. Along with the photopolymerization initiator, it can be produced by finely dispersing in a pigment carrier using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. The colored composition of the present invention can also be produced by mixing the pigments separately dispersed on the pigment carrier.
When dispersing the pigment in the pigment carrier, a dispersion aid such as a pigment derivative, a resin-type pigment dispersant, or a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency.

The pigment derivatives are compounds represented by the following general formula (6), and there are those having a basic substituent and those having an acidic substituent.
Formula (6)
AB
A: Organic pigment residue B: Basic substituent or acidic substituent In the formula (6), the organic pigment constituting the organic pigment residue of A includes diketopyrrolopyrrole pigments, azo, disazo, polyazo, etc. Azo pigments, copper phthalocyanine, halogenated copper phthalocyanine, phthalocyanine pigments such as metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, anthraquinone pigment, quinacridone Pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.

In the formula (6), examples of the basic substituent of B include substituents represented by the following formula (7), formula (8), formula (9), and formula (10). , Substituents represented by formula (11), formula (12), and formula (13).

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: The substituent shown by Formula (14) or the substituent shown by Formula (15) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (14) or a substituent represented by the formula (15). In the equation (14) and formula (15), R ₁ to R ₇ and n are the same as R ₁ to R ₇ and n in the formula (7) to (9).

Ｍ：水素原子、カルシウム原子、バリウム原子、ストロンチウム原子、マンガン原子またはアルミニウム原子を表す。
ｉ：Ｍの価数を表す。
Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃：それぞれ独立に、水素原子、置換されていてもよい炭素数１〜３６のアルキル基、置換されていてもよい炭素数２〜３６のアルケニル基、置換されていてもよいフェニル基またはポリオキシアルキレン基を表す。

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, or a substituent Represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used to form the substituent represented by the formulas (7) to (10), (14), and (15) 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, dideci Amine, 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, -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, 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.

  The amine component used to form the sulfonic acid amine salt of formula (13) may be any of primary, secondary, tertiary and quaternary amines. For example, primary amines have side chains. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, laurylamine, 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, dimethyldilaurylammonium 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 lauryl 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.

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

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium laurylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, lauryl sulfate monoethanolamine, 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 Nonionic surfactants such as alkyl 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, and these can be used alone or in admixture of two or more.

In the colored composition of the present invention, a 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 0.2 to 5 μm to form a filter segment. In order to facilitate the process, a solvent can be contained. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether 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, acetic acid Examples of the solvent include ethyl, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents. These are used alone or in combination.
The solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

Next, the color filter of the present invention will be described.
The color filter of the present invention is a color filter having filter segments formed using the colored composition of the present invention. The color filter includes an additive color mixture comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta filter segment, at least one cyan filter segment, And a subtractive color type with at least one yellow filter segment. In the color filter of the present invention, at least one color filter segment is formed using the colored composition of the present invention. Other filter segments may be formed using a colored composition containing only a photopolymerization initiator other than a photopolymerization initiator having 2 to 4 hydroxyl groups.

The red filter segment, the green filter segment, and the blue filter segment are formed using the above-described coloring composition containing the red pigment, the coloring composition containing the green pigment, and the coloring composition containing the blue pigment, respectively. Can do.
The magenta color filter segment is, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Pigment Red 144, 146, 177, 169, 81 and the like can be formed using a magenta coloring composition containing a violet pigment and a red pigment.
The cyan filter segment is, for example, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 81 and the like, and can be formed using a cyan coloring composition containing a blue pigment.

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

The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the coloring composition of this invention by the printing method or the photolithographic method.
As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate 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 is not dried and solidified 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 the solvent development type or alkali development type color resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist, 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, a water-soluble or alkaline water-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 colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming 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 formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.
First, preparation of acrylic resin solutions used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

[Preparation of acrylic resin solution]
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A polymer solution 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% by weight. Thus, a photosensitive resin solution was prepared. The weight average molecular weight of the obtained photosensitive resin was 40000.

Next, a treated pigment was produced by the following method.
The specific surface area of the pigment particles was determined by the BET method using nitrogen adsorption. In addition, the automatic vapor | steam adsorption amount measuring apparatus ("BELSORP18" by a Japanese bell company) was used for the measurement.
(Preparation of red treated pigment 1)
Red pigment C.I. I. Pigment Red 177 (“Chromophthaled A2B” manufactured by Ciba Specialty Chemicals, specific surface area 65 m ² / g): 500 parts, sodium chloride: 3500 parts, and diethylene glycol: 250 parts made of stainless steel 1 gallon kneader (Inoue Seisakusho) And kneaded at 120 ° C. for 8 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. As a result, red-treated pigment 1 was obtained. The specific surface area of the red treated pigment 1 was 90 m ² / g.

(Preparation of red treated pigment 2)
Red pigment C.I. I. Pigment Red 254 (“Irgafoa Red B-CF” manufactured by Ciba Specialty Chemicals, specific surface area 80 m ² / g): 500 parts, sodium chloride: 5000 parts, and diethylene glycol: 250 parts made of 1 gallon kneader made of stainless steel (Inoue And kneaded at 120 ° C. for 8 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. As a result, red-treated pigment 2 was obtained. The specific surface area of the red treated pigment 2 was 95 m ² / g.

(Preparation of green treated pigment 1)
Green pigment C.I. I. Pigment Green 36 (“Rionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd., specific surface area 55 m ² / g): 500 parts, sodium chloride: 750 parts, and diethylene glycol: 250 parts 1 gallon kneader made by stainless steel (manufactured by Inoue Seisakusho) And kneaded at 120 ° C. for 4 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. As a result, a green-treated pigment 1 was obtained. The specific surface area of the green treated pigment 1 was 69 m ² / g.

(Preparation of green treated pigment 2)
Green pigment C.I. I. Pigment Green 36 (“Rionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd., specific surface area 55 m ² / g): 500 parts, sodium chloride: 750 parts, and diethylene glycol: 250 parts 1 gallon kneader made by stainless steel (manufactured by Inoue Seisakusho) And kneaded at 120 ° C. for 8 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. As a result, green-treated pigment 2 was obtained. The specific surface area of the green treated pigment 2 was 78 m ² / g.

(Preparation of green treated pigment 3)
Green pigment C.I. I. Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Co., Ltd., specific surface area 55 m ² / g): 500 parts, sodium chloride: 1500 parts, and diethylene glycol: 250 parts made of stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) And kneaded at 120 ° C. for 8 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. As a result, green-treated pigment 3 was obtained. The specific surface area of the green treated pigment 3 was 85 m ² / g.

(Preparation of blue-treated pigment 1)
Blue pigment C.I. I. Pigment Blue 15: 6 (“Rionol Blue ES” manufactured by Toyo Ink Mfg. Co., Ltd., specific surface area 80 m ² / g): 500 parts, sodium chloride: 2500 parts, and diethylene glycol: 250 parts, 1 gallon kneader (made by Inoue Seisakusho) And kneaded at 120 ° C. for 12 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. As a result, blue-treated pigment 1 was obtained. The specific surface area of the blue-treated pigment 1 was 99 m ² / g.

アクリル樹脂溶液 ４０．０部
シクロヘキサノン ４８．０部 (Preparation of red pigment dispersion 1)
A mixture having the following composition was uniformly stirred and mixed, dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a red pigment dispersion.
Red treated pigment 1 12.0 parts 1.0 part of anthraquinone pigment derivative

Acrylic resin solution 40.0 parts Cyclohexanone 48.0 parts

(Preparation of red pigment dispersion 2)
A red pigment dispersion 2 was prepared in the same manner as the red pigment dispersion 1, except that the pigment was changed to the red-treated pigment 2 and the pigment derivative was changed to a diketopyrrolopyrrole pigment derivative having the following structure.

(Preparation of green pigment dispersion 1)
Pigment Green 36 (CI Pigment Green 36) (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.) 7.1 parts and monoazo pigment (CI Pigment Yellow 150) (“E4GN” manufactured by LANXESS) 3.9 parts A green pigment dispersion 1 was prepared in the same manner as the red pigment dispersion 1 except that the pigment derivative was changed to an azo pigment derivative having the following structure.

(Preparation of green pigment dispersion 2)
A green pigment dispersion 2 was produced in the same manner as the green pigment dispersion 1 except that the green pigment was changed to the green treated pigment 1.
(Preparation of green pigment dispersion 3)
A green pigment dispersion 3 was prepared in the same manner as the green pigment dispersion 1 except that the green pigment was changed to the green treated pigment 2.
(Preparation of green pigment dispersion 4)
A green pigment dispersion 4 was produced in the same manner as the green pigment dispersion 1 except that the green pigment was changed to the green treated pigment 3.

(Preparation of blue pigment dispersion 1)
Blue pigment dispersion 1 was prepared in the same manner as red pigment dispersion 1, except that the pigment was changed to blue-treated pigment 1 and the pigment derivative was changed to a phthalocyanine pigment derivative having the following structure.

[Examples 1 to 10 and Comparative Examples 1 to 8] (Preparation of colored composition)
With the blending composition shown in Table 1, the mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a colored composition.

Monomer: Trimethylolpropane triacrylate
(Shin Nakamura Chemical "NK Ester ATMPT")
Photopolymerization initiator A: 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one
("Irgacure 2959" manufactured by Ciba Specialty Chemicals)
Photopolymerization initiator B: 2-hydroxy-1- (4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl) -2-methyl-propan-1-one
("Irgacure 127" manufactured by Ciba Specialty Chemicals)
Photopolymerization initiator C: 1-hydroxycyclohexyl phenyl ketone
("Irgacure 184" manufactured by Ciba Specialty Chemicals)
Photopolymerization initiator D: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
("Irgacure 369" manufactured by Ciba Specialty Chemicals)

About the coloring composition obtained by the Example and the comparative example, developability, sensitivity, patterning property, and contrast ratio were evaluated by the following method.
(Developability evaluation)
The colored compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 8 were applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate to a thickness of 2 μm by spin coating. After pre-baking at 70 ° C. for 20 minutes, after developing with an alkaline developer at 23 ° C. for 30 seconds in the case of a red and blue colored composition coated substrate, and for 60 seconds in the case of a green colored composition coated substrate Washed with ion exchange water and air dried. The alkaline developer is 1.5% by weight of sodium carbonate, 0.5% by weight of sodium bicarbonate, 8.0% by weight of an anionic surfactant ("PERILEX NBL" manufactured by Kao) and 90% by weight of water. What was used.

The film thickness of the coated film after development was measured with a stylus type surface shape measuring instrument (“Dektak 8” manufactured by Veeco) and evaluated in four stages.
○: No coating film after development Δ: 0 μm <film thickness after development <0.2 μm
×: 0.2 μm ≦ film thickness after development <0.7 μm
XX: 0.7 μm ≦ film thickness after development

(Sensitivity evaluation)
The coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after pre-baking at 70 ° C. for 20 minutes, ultraviolet exposure was performed through a mask having a fine line pattern of 50 μm. Thereafter, this substrate was spray-developed using an alkali developer similar to that used in the evaluation of developability at 23 ° C. to remove unexposed portions, and then washed with ion-exchanged water and air-dried. The sensitivity of the coloring composition was determined by the irradiation exposure amount in which the pattern of the formed filter segment was finished according to the image size of the photomask. The rank of evaluation is as follows.
○: Less than 100 mJ / cm ² Δ: 100 mJ / cm ² or more and less than 300 mJ / cm ² ×: 300 mJ / cm ² or more

(Patternability evaluation)
In the sensitivity evaluation, the same method was used except that the exposure amount of ultraviolet rays was the saturation exposure amount + 50 mJ / cm ² , and the development time with an alkali developer was an appropriate time to wash away the unexposed portions of the respective resist coating films. After preparing the substrate, the substrate was heat-treated at 230 ° C. for 60 minutes, and the shape of the fine line pattern was evaluated by (1) the linearity of the pattern and (2) the cross-sectional shape of the pattern.
About (1), visual evaluation was performed using the 500 times optical microscope. The rank of evaluation is as follows.
○: Good linearity Δ: Partially good linearity ×: Poor linearity

(2) was evaluated by observing a cross section with a 10,000 times scanning electron microscope (SEM). The rank of evaluation is as follows.
○: Forward tapered shape.
Δ: Non-tapered shape.
X: Reverse taper shape.

(Evaluation of contrast ratio)
About the coloring composition application | coating board | substrate, the contrast ratio was measured with the following method using the measuring apparatus shown in FIG. The results are shown in Table 1.
A coloring composition coating substrate is sandwiched between two polarizing plates, and light is irradiated from one polarizing plate side using a backlight unit (7) for liquid crystal display. The light emitted from the backlight unit passes through the first polarizing plate (6) and is then polarized, and then passes through the colored composition coated substrates (4) and (5), and the second polarizing plate (3). To reach. If the polarization planes of the first polarizing plate and the second polarizing plate are parallel, light passes through the first polarizing plate, but if the polarization plane is perpendicular, the light passes through the second polarizing plate. Are blocked by the polarizing plate. However, when the light polarized by the first polarizing plate passes through the resist material coated substrate, scattering by pigment particles or the like causes a deviation in a part of the polarization plane. When the amount of light transmitted through the second polarizing plate is reduced and the deflecting plate is perpendicular, a part of the light is transmitted through the second polarizing plate. The luminance of the transmitted light is measured with a luminance meter (1) on the polarizing plate, and the ratio of the luminance when the polarizing plate is parallel to the luminance when the polarizing plate is perpendicular is taken as the contrast ratio.

Contrast ratio = (Luminance when parallel) / (Luminance when direct)
Accordingly, when scattering occurs due to the pigment in the colored composition coating film, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.
The luminance meter used was “Color Luminance Meter BM-5A” manufactured by Topcon Corporation, and the polarizing plate used was “Polarized Film LLC2-92-18” manufactured by Sanritsu. 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に示すように、２〜４個の水酸基を有する光重合開始剤を用いた実施例１〜１０の着色組成物は、現像性が良好であり、感度、得られたパタ−ンの直線性および断面形状も良好であったのに対し、２〜４個の水酸基を有する光重合開始剤を用いていない比較例１〜８の着色組成物は、現像性、感度、パタ−ンの直線性および断面形状のいずれかが不良であり、全てが良好となるものは得られなかった。

As shown in Table 2, the coloring compositions of Examples 1 to 10 using a photopolymerization initiator having 2 to 4 hydroxyl groups have good developability, sensitivity, and a straight line of the obtained pattern. The coloring compositions of Comparative Examples 1 to 8, which did not use a photopolymerization initiator having 2 to 4 hydroxyl groups, were good in developability, sensitivity, and pattern. Any of the properties and the cross-sectional shape were poor, and none of them was satisfactory.

It is a conceptual diagram of the apparatus which measures the contrast ratio of a coloring composition application | coating board | substrate.

Explanation of symbols

(1) Luminance meter (2) Mask (3) Polarizing plate (4) Resist coating film (5) Glass (6) Polarizing plate (7) Backlight unit

Claims (8)

A pigment carrier formed of a transparent resin and a precursor thereof, a pigment, and two photopolymerization initiator having a hydroxyl group, further comprise other photoinitiators, photo-polymerization initiator and the other having two hydroxyl groups The weight ratio with respect to the photopolymerization initiator is 5:95 to 20:80 , and the pigment is a pigment having a specific surface area controlled by a grinding method, a precipitation method, or a synthetic precipitation method. Coloring composition for color filter. The coloring composition for a color filter according to claim 1, wherein the pigment is a red pigment having a specific surface area of 85 to 130 m ² / g.   The red pigment is C.I. I. Pigment Red 177 and / or C.I. I. The coloring composition for a color filter according to claim 2, which is Pigment Red 254. The coloring composition for a color filter according to claim 1, wherein the pigment is a green pigment having a specific surface area of 60 to 100 m ² / g.   The green pigment is C.I. I. Pigment Green 7 and / or C.I. I. The coloring composition for a color filter according to claim 4, which is Pigment Green 36. The coloring composition for a color filter according to claim 1, wherein the pigment is a blue pigment having a specific surface area of 90 to 140 m ² / g.   The blue pigment is C.I. I. The coloring composition for a color filter according to claim 6, which is Pigment Blue 15: 6.   A color filter comprising a filter segment formed from the colored composition according to claim 1.

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