JP2009161686A - Colored resin composition, forming method of colored picture element, manufacturing method of color filter, and color display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored resin composition capable of giving a coat film showing excellent surface uniformity with little unevenness even when an ink jet method is used, and to provide a forming method of a colored picture image, a manufacturing method of a color filter and a color display device. <P>SOLUTION: The colored resin composition used for forming the colored picture image in the manufacture of the color filter contains a pigment (A), a pigment-dispersive resin (B) and an organic solvent (C) wherein the organic solvent (C) is 1,6-hexanol diacetate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored resin composition, a method for forming a colored image, a method for producing a color filter, and a color display device, and more specifically, is formed by an ink jet method, and a coating film shape with few irregularities and excellent surface uniformity is obtained. The present invention relates to a colored resin composition, a colored image forming method, a color filter manufacturing method, and a color display device.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal display devices, particularly color liquid crystal display devices, has been increasing.
However, since this color liquid crystal display device is expensive, there is an increasing demand for cost reduction. In particular, there is a high demand for cost reduction for a color filter having a high specific gravity.

  In such a color filter, usually, a coloring pattern of three primary colors of red (R), green (G), and blue (B) is provided, and electrodes corresponding to R, G, and B pixels are turned on and off. Then, the liquid crystal operates as a shutter, and light passes through each of the R, G, and B pixels, and color display is performed.

  As a conventional method for producing a color filter, for example, a staining method can be mentioned. In this dyeing method, first, a water-soluble polymer material, which is a dyeing material, is formed on a glass substrate, patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To get a colored pattern. By repeating this three times, R, G and B color filter layers are formed.

  Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers.

  However, in such a color filter manufacturing method using the photolithography method, the yield is reduced by complicated processes, the power consumption is increased by performing post-baking at a high temperature three times, and the waste liquid by the spin coating method is a barrier to cost reduction. In addition, there is a problem of a decrease in production efficiency.

In recent years, in order to solve these problems, a technique of forming colored pixels from a conventional photolithography method using an inkjet method has attracted attention as a new method for manufacturing a color filter.
The ink jet method is a very simple coloring method in which color ink necessary for coloring is ejected from a nozzle in a desired amount to a desired position for printing. Therefore, it can be expected that the yield is improved by shortening the exposure and development processes, the power consumption is reduced by RGB batch post-baking, and the amount of liquid used is reduced.
On the other hand, in these ink jet methods, the yield and production efficiency are greatly affected by the characteristics of the colored resin composition. The properties required for the colored resin composition include droplet discharge properties and surface uniformity, and further improvements in these properties are required.
Until now, various attempts have been made to improve the characteristics of color inks compatible with the inkjet method, such as using specific solvents, colorants, and surfactants (see, for example, Patent Documents 1 and 2). A sufficient effect has not been obtained.

JP 2007-204662 A JP 2007-256865 A

  An object of the present invention is to provide a colored resin composition, a colored image forming method, and a color filter that can obtain a coating film shape with few irregularities and excellent surface uniformity even when an ink jet method is used. A manufacturing method and a color display device are provided.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a coating film shape with few irregularities and excellent surface uniformity by using a colored resin composition containing a specific solvent. The present invention has been reached.
That is, this invention provides the following colored resin composition, the formation method of a colored image, the manufacturing method of a color filter, and a color display apparatus.

1. A colored resin composition containing (A) a dye, (B) a dye-dispersible resin, and (C) an organic solvent, wherein (C) the organic solvent contains 1,6-hexanol diacetate. Resin composition.
2. (B) The colored resin composition according to 1 above, wherein the dye-dispersible resin is a (meth) acrylic resin having a mass average molecular weight of 1,500 to 200,000.
3. Furthermore, (D) 1 or 2 colored resin composition containing the polymeric compound which has an ethylenically unsaturated group.
4). Furthermore, the coloring resin composition in any one of said 1-3 containing (E) photoinitiator.
5. 4. The remaining component is mixed in a pigment dispersion obtained by mixing (A) a pigment, (B) a portion of a pigment-dispersible resin and (C) a portion of an organic solvent. A method for producing a colored resin composition.
6). A colored pixel forming method, wherein a colored pixel is formed by an ink jet method using any one of the colored resin compositions 1 to 4 above.
7). A method for producing a color filter, comprising the step of forming a colored pixel on a substrate by an inkjet method using the colored resin composition according to any one of 1 to 4 above.
8). A color display device comprising a color filter produced by the method described in 7 above.
9. 8. The color display device according to 8 above, which has a liquid crystal display provided with a color filter manufactured by the method 7 above.

  According to the present invention, there is provided a colored resin composition which is formed by an ink jet method and forms a colored pixel with less surface irregularities and good surface uniformity. Therefore, according to the present invention, it is possible to efficiently provide a color filter, a color display device, and a color liquid crystal display device each having a good quality image.

Hereinafter, the present invention will be described in detail.
(1) Colored resin composition The colored resin composition of the present invention is a colored resin composition containing (A) a dye, (B) a dye-dispersible resin, and (C) an organic solvent, and further has photosensitivity. (D) a polymerizable compound having an ethylenically unsaturated group, and (E) a photopolymerization initiator.
Next, each component of the colored resin composition of the present invention will be described.

(A) Dye Although both dye and pigment can be used for the (A) dye of the present invention, a pigment is more preferable in consideration of heat resistance and light resistance. The pigment includes inorganic pigments and organic pigments, and both can be used, but black carbon black (inorganic pigment) and organic pigments are preferred because of their rich color tone. Examples of the organic pigment include azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine / azomethine, and isoindolinone. When producing the color filter of the present invention, each pigment system suitable for colored images such as red, green, blue and black is used.

For a red colored image, a single red pigment may be used, or toning may be performed by mixing a yellow or orange pigment with a red pigment.
Examples of the red pigment include pigment red 1, 2, 5, 9, 17, 31, 32, 41, 122, 123, 144, 149, 155, 166, 168, 170, 171, 176, and 177 as color index names. 178, 179, 180, 185, 187, 202, 206, 207, 209, 214, 217, 220, 221, 224, 242, 243, 254, 255, 262, 264, 272 and the like.
Examples of the yellow pigment include, for example, pigment yellow 12, 13, 14, 17, 20, 24, 31, 55, 83, 93, 109, 110, 117, 125, 128, 129, 138, and 139 as color index names. 147, 150, 153, 154, 155, 166, 168, 180, 211 and the like.
Examples of the orange pigment include pigment orange 5, 13, 14, 24, 34, 36, 38, 40, 43, 46, 49, 61, 64, 68, 70, 71, 72, 73, 74 by color index name. Etc.
These red, yellow and orange pigments can be used in combination of two or more. When a red pigment and a yellow pigment are mixed and used, it is preferable to use a yellow or orange pigment at 90 parts by mass or less with respect to 100 parts by mass of the total amount of the red pigment and the yellow pigment.

For a green colored image, a single green pigment may be used, or toning may be performed by mixing a yellow pigment into a green face system. Examples of the green pigment include zinc phthalocyanine and a halide thereof in which the metal part of copper phthalocyanine is changed from copper to zinc, such as pigment green, 7, 36, 37, 136, and 137 by color index name. Examples of the yellow pigment to be mixed include those described above.
Two or more of these green and yellow pigments can be mixed and used. When a green pigment and a yellow pigment are mixed and used, the yellow pigment is preferably used in an amount of 90 parts by mass or less with respect to 100 parts by mass of the total amount of the green pigment and the yellow pigment.

For a blue colored image, a single blue pigment may be used, or toning may be performed by mixing a purple pigment with a blue pigment. Examples of the blue pigment include Pigment Blue 15, 15: 3, 15: 4, 15: 6, 22, 40, 60, 76, 80 and the like by color index name. Moreover, as a purple pigment, pigment violet 10, 19, 23, 29, 37, 50 etc. are mentioned by a color index name, for example.
These blue and purple pigments can be used in combination of two or more. Moreover, when using a mixture of a blue pigment and a purple pigment, it is preferable to use the purple pigment at 90 parts by mass or less with respect to 100 parts by mass of the total amount of the blue pigment and the purple pigment.

Examples of black colored images include carbon black, graphite, titanium black, black iron oxide, manganese dioxide, and the like. I. Pigment black 1, C.I. I. Pigment Black 7 black pigment is used.
The content of the (A) dye in the colored resin composition of the present invention is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 15 to 15% in the total solid content of the colored resin composition. 55% by mass. (A) By making a pigment | dye 5 mass% or more, the color density of an image does not become low, By making it 70 mass% or less, inkjet droplet clogging can be prevented.
In the present invention, the “solid content” means a nonvolatile content, that is, an evaporation residue.

(A) The pigment used as a pigment | dye can be used with a dispersing agent. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl Polyoxyethylene alkyl phenyl ethers such as ethers; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid-modified polyesters; Tertiary amine-modified polyurethanes; Polyethyleneimines Can do.
In addition, as a trade name of the surfactant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), MegaFac (manufactured by Dainippon Ink & Chemicals, Inc. ), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Disperbyk (manufactured by Big Chemie Japan Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.) And the like.
These surfactants can be used alone or in admixture of two or more. The amount of the dispersant used is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the pigment.

(B) Dye dispersible resin (B) The dye dispersible resin in the colored resin composition of the present invention is not particularly limited as long as it has a dye dispersibility when used as a colored image forming material. It is preferable to have a photosensitivity.
Examples of such a dye-dispersible resin include (meth) acrylic acid esters (acrylic acid esters and methacrylic acid esters) such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. (Meth) acrylic resin composed of a homopolymer or a copolymer of the following) is preferably used.
In particular, (meth) acrylic resin, at least two types of monomer components are (I) 2-hydroxyethyl methacrylate and (II) methacrylic acid, and (III) one or more benzene rings in the unit molecule. When a copolymerizable (meth) acrylic monomer is used as a raw material and the copolymer resin of (I), (II) and (III) is 100 parts by mass, (I) 2-hydroxyethyl methacrylate is 3-30 parts by mass, (II) A copolymer resin comprising 5 to 50 parts by weight of methacrylic acid and (III) 20 to 92 parts by weight of a copolymerizable (meth) acrylic monomer having one or more benzene rings in the unit molecule is a pigment. It is preferable from the viewpoint of dispersion stability and photosensitivity.

  (B) Cellulosic resins such as carboxymethyl hydroxyethyl cellulose and hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and the like can also be used as the dye-dispersing resin, and styrene; styrene derivatives; homopolymers of other polymerizable monomers or Copolymers, carboxyl group-containing polymerizable monomers such as (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic anhydride, citraconic acid monoalkyl ester, and (meth) Acrylic esters, styrene, styrene derivatives, copolymers with other polymerizable monomers, and the like can also be suitably used.

  The maleic acid monoalkyl ester is preferably an alkyl group having 1 to 12 carbon atoms, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate, mono-n-maleate. Examples include butyl, mono-n-hexyl maleate, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate, and the like.

As the citraconic acid monoalkyl ester, those having 1 to 12 carbon atoms in the alkyl group are preferable, and citraconic acid monomethyl, citraconic acid monoethyl, citraconic acid mono-n-propyl, citraconic acid monoisopropyl, citraconic acid mono-n- Examples thereof include butyl, mono-n-hexyl citraconic acid, mono-n-octyl citraconic acid, mono-2-ethylhexyl citraconic acid, mono-n-nonyl citraconic acid, and mono-n-dodecyl citraconic acid.
Examples of the styrene derivative include α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene, and the like.

  Further, as the (B) dye-dispersible resin, a resin having a photopolymerizable unsaturated bond is also suitable. Preferable examples of such a dye-dispersible resin include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and itaconic acid monoalkyl glycidyl ether. Compounds having one oxirane ring and one ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxy A resin obtained by reacting a compound (unsaturated alcohol) having a hydroxyl group and one ethylenically unsaturated bond, such as ethyl methacrylate or N-methylolacrylamide, and a carboxyl group-containing resin having a hydroxyl group. Resins obtained by reacting isocyanate group-containing unsaturated compounds, resins obtained by reacting polybasic acid anhydrides with addition reaction products of epoxy resins and unsaturated carboxylic acids, conjugated diene polymers or conjugated diene copolymers and unsaturated dicarboxylic acids Examples thereof include a resin obtained by reacting an addition reaction product with an acid anhydride with a hydroxyl group-containing polymerizable monomer.

  The unsaturated equivalent of the resin having a photopolymerizable unsaturated bond is preferably 100 to 3,000, more preferably 200 to 2,500, and particularly preferably 600 to 2,000. By setting the unsaturated equivalent to 100 or more, when the coloring material is prepared, particularly when the pigment is dispersed in the resin, there is no partial curing, and by setting the unsaturated equivalent to 3,000 or less, the unsaturated equivalent Photopolymerizability due to the introduction of the group is sufficiently imparted. The unsaturated equivalent here means the molecular weight of the resin per unsaturated bond.

  (B) The mass average molecular weight of the dye-dispersible resin is preferably in the range of 1,500 to 200,000, more preferably in the range of 3,000 to 100,000, and in the range of 5,000 to 50,000. Particularly preferred. By setting the mass average molecular weight to 1,500 or more, the droplets can be discharged without being scattered, and by setting the mass average molecular weight to 200,000 or less, the droplets are not clogged. The mass average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

Moreover, as (B) dye-dispersible resin used for the colored resin composition of this invention, you may use together the dye-dispersible resin mentioned above and other resin. Examples of other resins include polyimide resins, acrylic resins, epoxy resins, urethane resins, and melamine resins. However, the other resin is preferably used in an amount of 50% by mass or less in the total amount of the (B) dye-dispersible resin. Moreover, when using the said thermosetting resin, you may use a hardening | curing agent together as needed. Curing agents include amines (aliphatic amines, aromatic amines, modified amines, etc.), polyamide resins (polyamide amines, etc.), tertiary and secondary amines (piperazine, N, N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, etc.) ), Imidazoles (2-methylimidazole, 2-ethyl-4-methylimidazole, etc.), mercaptan curing agents (liquid polymercaptan, polysulfide resin, etc.), acid anhydrides, latent curing agents (boron trifluoride-amine) Complex, dicyandiamide, organic acid hydrazide, and the like), but are not limited to the above curing agents, and other known ones can also be used.
The content of the (B) dye-dispersible resin in the colored resin composition of the present invention is preferably 10 to 85 mass%, more preferably 20 to 60 mass%, particularly preferably in the total solid content of the colored resin composition. Is 25-50 mass%. (B) Dispersion stability of the pigment is not lowered by setting the pigment-dispersible resin to 10% by mass or more, and viscosity can be increased or ejection properties can be lowered by setting the pigment-dispersible resin to 85% by mass or less. Absent.

(C) Organic solvent The colored resin composition of the present invention is applied with a coating solution using an organic solvent in order to apply it onto a substrate using an inkjet method. The (C) organic solvent of the colored resin composition of the present invention contains 1,6-hexanol diacetate.

  Examples of organic solvents other than the above include ketone compounds, alkylene glycol ether compounds, alcohol compounds, and aromatic compounds. Specifically, the ketone compound includes acetone, methyl ethyl ketone, cyclohexanone, and the like, and the alkylene glycol ether compound includes methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene Glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene Glycol monomethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol-t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, Examples include triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, triethylene glycol butyl ether acetate, and triethylene glycol-t-butyl ether acetate. Methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol, etc., and aromatic compounds include benzene, toluene, xylene, N-methyl-2-pyrrolidone, N-hydroxy Examples thereof include methyl-2-pyrrolidone, and others include 3-methyl-3-methoxybutyl acetate, ethyl acetate, tetrahydrofuran, dioxane and the like. These can be used alone or in combination of two or more.

These organic solvents can be used alone or in combination of two or more of 1,6-hexanol diacetate and other organic solvents.
1,6-hexanol diacetate is preferably used in the range of 5 to 100% by mass in the total amount of the organic solvent, and more preferably in the range of 10 to 100% by mass. By setting the content to 5% by mass or more, it is possible to improve ink jetting properties.
The organic solvent is preferably used so that the total content of solid components in the colored resin composition is in the range of 5 to 30% by mass. By setting it to 30% by mass or less, it is possible to prevent the viscosity from becoming high and to prevent clogging of droplets. By setting it as 5 mass% or more, it can prevent that the film thickness which can be formed by one drop becomes thin.

(D) Polymerizable compound having an ethylenically unsaturated group The colored resin composition of the present invention has (D) an ethylenically unsaturated group in order to improve reactivity, particularly when it is photosensitive. It is preferable to contain a polymerizable compound. (Hereinafter, EO means ethylene oxide, PO means propylene oxide, and ECH means epichlorohydrin.)
(D) Examples of the polymerizable compound having an ethylenically unsaturated group include methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxytriethylene glycol acrylate, ECH-modified butyl acrylate, dicyclopentanyl acrylate, and EO-modified dicyclopentenyl. Acrylate, N, N-dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone modified-2-hydroxyethyl acrylate, isobornyl acrylate, methoxy Dipropylene glycol acrylate, methoxylated cyclodecatriene acrylate, Enoxyhexaethylene glycol acrylate, EO-modified phosphoric acid acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, EO-modified bisphenol A diacrylate, ECH-modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1 , 3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO-modified phosphoric acid diacrylate, ECH-modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate, tetraethylene Glycol diacrylate, ECH-modified 1,6-hexanediol dia Lilate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphoric acid triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, tris (methacryloxyethyl) isocyanurate, tris (2-acryloyl) And acrylates such as (oxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the corresponding methacrylates. One or more of these compatibility compounds can be used in combination.
(D) The content of the polymerizable compound having an ethylenically unsaturated group is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 10% by mass in the total amount of solid components of the colored resin composition. 30% by mass.

(E) Photopolymerization initiator In the colored resin composition of the present invention, when (D) a polymerizable compound having an ethylenically unsaturated group is used as a polymerizable compound having photosensitivity, in order to increase photosensitivity ( E) It is preferable to contain a photopolymerization initiator. (E) As the photopolymerization initiator, for example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, Benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, , 10-phenanthraquinone, 1,2-anthraquinone, 1,4-dimethyl anthraquinone, 2-phenyl anthraquinone, 2- (o-chlorophenyl) -4,5 the like and diphenyl imidazole dimer. These photoinitiators are used individually or in combination of 2 or more types.
The content of the (E) photopolymerization initiator in the colored resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 1 to 15% by mass, in the total amount of solid components of the colored resin composition. Especially preferably, it is 2-10 mass%.

  In addition, the colored resin composition of the present invention includes a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing dark reaction, and a cup for improving adhesion to the substrate. Ring agent (silane coupling agent having vinyl group, epoxy group, amino group, mercapto group, isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.), interface for improving the smoothness of the film Activators (fluorine-based, silicon-based, hydrocarbon-based, etc.) and other additives such as ultraviolet absorbers and antioxidants can be used as necessary.

(2) Method for Producing Colored Resin Composition For the production of the colored resin composition of the present invention, usually, first, (A) the dye, (B) the dye-dispersible resin, (C) the organic solvent, and, if necessary, the dispersant And dispersed to produce a pigment dispersion. The mixture is dispersed by kneading using a dispersing / kneading device by kneading using a dispersing / kneading device such as an ultrasonic dispersing machine, three rolls, ball mill, sand mill, bead mill, homogenizer, kneader or the like. Is preferred.
When producing a pigment dispersion by dispersion treatment, it is preferable to use 20 parts by mass or more of (B) the pigment-dispersible resin with respect to 100 parts by mass of (A) the pigment. By setting it to 20 parts by mass or more, dispersion stability of a pigment such as a pigment can be obtained. Moreover, it is preferable to use 100 mass parts or more of (C) the organic solvent with respect to 100 mass parts of the total amount of the (A) dye and the (B) dye-dispersible resin at the time of dispersion. By setting it as 100 mass parts or more, the dispersion | distribution in the case of disperse | distributing especially with a ball mill, a sand mill, a bead mill etc. can be made easy.

The (D) photopolymerizable compound and the (E) photopolymerization initiator may be mixed before the dispersion treatment of the dye in the (B) dye-dispersible resin, or may be mixed after the dispersion treatment.
(B) The dye-dispersible resin may be used in its entirety with the dye during the dispersion treatment, or a part thereof may be added after the dispersion treatment. Similarly, the total amount of the organic solvent (C) may be used together with the pigment during the dispersion treatment, or a part thereof may be added after the dispersion treatment.
The amount of each component used is adjusted so that the blending ratio in the colored resin composition is finally reached.

  Dispersants include anionic dispersants such as polycarboxylic acid type polymer surfactants, polysulfonic acid type polymer surfactants, nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers, anthraquinone type, perylene. And organic dye derivatives in which a substituent such as a carboxyl group, a sulfonate group, a carboxylic acid amide group, or a hydroxyl group is introduced into an organic dye such as phthalocyanine, phthalocyanine, or quinacridone. These dispersants can be used alone or in admixture of two or more. By using a dispersant, the dispersibility and dispersion stability of the dye are improved. The amount of the dispersant used is usually 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the dye. By setting it to 50 parts by mass or less, the tendency of chromaticity shift can be suppressed.

As a preferable embodiment of the method for producing the colored resin composition, (A) the total amount of the dye, (B) a part of the dye-dispersing resin, and (C) a part of the organic solvent are mixed to prepare a colored dye dispersion. The remaining components, that is, the remaining (B) dye-dispersible resin and the remaining (C) organic solvent and optionally used (D) photopolymerizable compound and (E) photopolymerization start The method of mixing with an agent is mentioned.
As in the above method, the mixing of (B) the dye-dispersing resin and (C) the organic solvent is divided into two, and after preparing the dye dispersion, the photopolymerizable compound is mixed to prepare the colored resin composition. As a result, the dispersibility of the dye can be improved, and the pixel characteristics can be improved.

(3) Colored Pixel Forming Method, Color Filter and Manufacturing Method Thereof The colored resin composition of the present invention can be used for manufacturing colored pixels and color filters.
First, when it is used for forming colored pixels, an inkjet method is used. Pixels can be formed by discharging the colored resin composition of the present invention onto a substrate. Moreover, in order to manufacture the color filter of this invention, the formation method of the above-mentioned colored pixel can be integrated as a process of forming a colored pixel.

When producing the color filter of the present invention, pigments such as pigments suitable for colored images such as red, green, blue and black are used.
The substrate is selected depending on the application, for example, a transparent glass plate such as white plate glass, blue plate glass, silica coated blue plate glass, a sheet made of synthetic resin such as polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin, film or Examples thereof include a metal plate such as a plate, an aluminum plate, a copper plate, a nickel plate, and a stainless plate, a ceramic plate, and a semiconductor substrate having a photoelectric conversion element. On these substrates, a black matrix may be formed in advance by chromium vapor deposition or black photosensitive colored resin composition.

A substrate coated with a colored resin composition using an inkjet method is preferably post-baked after coating to harden the colored pixels more firmly. The post-baking temperature is preferably 60 to 280 ° C., and the heating time is preferably about 1 to 60 minutes. Further, it may be dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes or preliminarily dried by vacuum drying and then post-baked.
The thickness of the coating film thus formed is appropriately determined depending on the application, but is preferably in the range of 0.1 to 300 μm. Moreover, when using for a color filter, it is preferable to set it as the range of 0.2-5 micrometers.

When the coating film formed on the substrate has photosensitivity, exposure may be performed before post-baking. The photosensitive layer formed on the substrate can be exposed by irradiating the photosensitive layer with an actinic ray in an image form. In general, the amount of light during exposure is preferably 10 to 500 mJ / cm ² . Thereby, the film | membrane of an exposure part can be hardened.
As the actinic ray light source, for example, a carbon arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a visible light laser, and the like are suitable. By using these light sources and performing pattern exposure through a photomask or direct drawing by scanning, actinic rays are irradiated in an image form.

In this way, a colored pixel can be obtained. In particular, in the production of a color filter, the process of forming a colored pixel by the colored pixel production method of the present invention is repeated for different colored pixels of 3 to 4 colors or different. 3 to 4 colored pixels can be formed simultaneously. For example, red, green and blue colored pixels are formed sequentially or simultaneously on a black matrix previously formed by chromium vapor deposition or the like. And it can form by performing the post-baking similar to the above.
Furthermore, after forming colored pixels of red, green, and blue, a black matrix may be formed using a black pixel forming material in a gap between these colored pixels. The order of forming red, green, and blue colored pixels is arbitrary.

(4) Color display device, color liquid crystal display device The color display device of the present invention has a color filter manufactured by the above method, and uses a liquid crystal display device having a color filter manufactured by the method. Including a color display device.
In the case of a color display device using such a liquid crystal display device, a colored pixel is usually formed on a substrate by the above-described method, and sandwiched between the planarizing layer, the electrode, and the alignment film by a resin or the like covering the surface. A liquid crystal cell having a liquid crystal layer, and if necessary, a polarizing film, a reflection plate, a phase difference plate, a light source, and the like are disposed outside the liquid crystal cell and used as a liquid crystal element.
Specific examples of such a color display device include a field emission display device, a fluorescence display device, an organic electroluminescence color display, a plasma display (PDP), and a liquid crystal display.

EXAMPLES Next, although an Example demonstrates this invention in more detail, these Examples do not restrict | limit this invention.
In addition, the colored resin composition obtained by the following example and the comparative example evaluated the coating-film shape unevenness | corrugation with the following method.

(Evaluation method for coating film unevenness)
The colored resin composition obtained in each example and comparative example was ejected onto a glass substrate (product name 7059, manufactured by Corning) using an inkjet apparatus using a piezo conversion method and a nozzle diameter of 50 × 80 μm. Further, the organic solvent was evaporated by carrying out at 100 ° C. for 5.0 minutes, and then the post-baking was cured by heating at 230 ° C. for 40 minutes to form a blue coating film. The shape of the obtained blue coating film was measured using a surface shape measuring instrument (Dektak ³ ST, manufactured by Nippon Vacuum Technology Co., Ltd.), and the shape unevenness was observed.

Example 1
(1) Production of Dye Dispersible Resin These are copolymerized so as to be 70% by mass of benzyl methacrylate, 15% by mass of 2-hydroxyethyl methacrylate and 15% by mass of methacrylic acid, and have a weight average molecular weight of 24,000 and an acid value of 96. A dye dispersible resin comprising a copolymer of (mg [KOH] / g) was produced.

(2) Production of Blue Dye Dispersion 0.7 g of the dye-dispersing resin obtained in (1), 13.1 g of Pigment Blue 15: 6 as the dye, and Solsperse [manufactured by Geneca Co., Ltd.] 4 as the dispersant .8 g and 81.4 g of propylene glycol monomethyl ether acetate as an organic solvent were mixed and dispersed for 2 hours using a bead mill to prepare a blue pigment dispersion.

(3) Production of colored resin composition 40.1 g of blue dye dispersion, 19.0 g of dye-dispersing resin, 4.7 g of dipentaerythritol hexaacrylate as a polymerizable compound having an ethylenically unsaturated group, and 1 as an organic solvent , 6-hexanol diacetate 36.2g was mixed to prepare a colored resin composition.
The result of having evaluated the coating-film shape unevenness | corrugation by the said method about the obtained colored resin composition is shown in FIG.

Comparative Example 1
The production of the colored resin composition of Example 1 (3) was carried out in the same manner as in Example 1 except that dipropylene glycol monobutyl ether was used instead of 1,6-hexanol diacetate as the organic solvent.
FIG. 2 shows the result of evaluating the unevenness of the coating film shape by the above method for the obtained colored resin composition.

Comparative Example 2
The production of the colored resin composition of Example 1 (3) was carried out in the same manner as in Example 1 except that diethylene glycol monobutyl ether acetate was used in place of 1,6-hexanol diacetate as the organic solvent.
FIG. 3 shows the results of evaluating the coating film unevenness of the obtained colored resin composition by the above method.

1 to 3, it is confirmed that in Example 1, a colored image with less coating film shape unevenness and excellent surface uniformity is obtained as compared with Comparative Examples 1 and 2.
Therefore, according to the present invention, a color display device having an excellent colored image formed by the ink jet method is efficiently manufactured.

The evaluation result of the coating-film shape unevenness | corrugation in the colored resin composition of Example 1 is shown. The evaluation result of the coating-film shape unevenness | corrugation in the colored resin composition of the comparative example 1 is shown. The evaluation result of the coating-film shape unevenness | corrugation in the colored resin composition of the comparative example 2 is shown.

Claims (9)

  A colored resin composition containing (A) a dye, (B) a dye-dispersible resin, and (C) an organic solvent, wherein (C) the organic solvent contains 1,6-hexanol diacetate. Resin composition.   The colored resin composition according to claim 1, wherein (B) the dye-dispersible resin is a (meth) acrylic resin having a mass average molecular weight of 1,500 to 200,000.   The colored resin composition according to claim 1 or 2, further comprising (D) a polymerizable compound having an ethylenically unsaturated group.   Furthermore, the coloring resin composition in any one of Claims 1-3 containing (E) photoinitiator.   5. The remaining component is mixed with a pigment dispersion obtained by mixing (A) a pigment, (B) a part of a pigment-dispersible resin and (C) a part of an organic solvent. The manufacturing method of the coloring resin composition as described in any one of.   A colored pixel forming method, wherein the colored pixel composition is formed by an inkjet method using the colored resin composition according to claim 1.   A method for producing a color filter, comprising a step of forming a colored pixel on a substrate by an inkjet method using the colored resin composition according to claim 1.   A color display device comprising a color filter manufactured by the method according to claim 7.   The color display device according to claim 8, comprising a liquid crystal display provided with a color filter manufactured by the method according to claim 7.

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