JPH09292516A - Production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a color filter having high density by spraying a specified ink compsn. by an ink-jet method on a transparent substrate having a specified polymer crosslinked layer, then drying and treating the sprayed material with water. SOLUTION: An ink compsn. prepared by dissolving an anion dye in an amide solvent soln. is sprayed by an ink-jet method on a transparent substrate having a polymer crosslinked layer which can be dyed with anion dyes. The sprayed material is dried and treated with water. As for the amide solvent, a compd. having no active hydrogen is preferable considering the dyeing property, and especially N-methylpyrrolidone is preferable. The amt. of the amide solvent in the ink compsn. is preferably 3 to 40wt.%. The density of the anion dye in the ink compsn. is preferably 1 to 10%. The polymer which can be dyed with anion dyes is preferably a resin having tertiary amino groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a color filter having excellent optical characteristics used in liquid crystal display devices, color separation devices, sensors and the like.

[0002]

2. Description of the Related Art Conventionally, a method of combining three primary color filters of red, green, blue, or yellow, magenta, and cyan has been used for colorizing a liquid crystal display device or a solid-state image pickup device. Although there are several methods for forming these color filters, the most basic method is the so-called dyeing method. The color filter is produced by a dyeing method, which is a film of a synthetic resin having a thin film-like transparent cationic group such as a stripe or mosaic (referred to as a pattern) on the surface of a substrate such as glass or silicon wafer. Alternatively, the basic principle is to provide a film of a protein-based natural polymer such as gelatin, casein, or glue to form a film to be colored, and dye (color) this with a dye. The following three methods are known as specific manufacturing processes of the color filter.

(1) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer. Then a non-coloring protective coat
A coating film is provided on the entire surface, and a second coating film to be colored is provided thereon by the same operation as above. Hereinafter, if necessary, colored layers are sequentially laminated.

(2) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer, and then a dye is fixed with tannic acid or the like. Combined with dye-proof treatment. A second coating to be colored is provided by the same operation. Thereafter, if necessary, a colored layer is formed on the same substrate surface.

(3) A film to be colored (coloring film) is provided on the surface of the substrate. After providing a positive resist layer thereon, the film to be colored is exposed and developed through a mask to dye the exposed film to be colored, and then the positive resist layer is peeled off to form a colored portion. By repeating the operation after providing the positive resist layer, the same colored film is dyed into a desired pattern in a plurality of colors.

Color produced by the above process
Except for special ones, the filters are usually the three primary colors R (red), G (green), B (blue) or the complementary three primary colors Y (yellow), M (magenta), C (cyan). ), (M may be omitted). The most important characteristic required for the color filter is the optical characteristic, and the spectral characteristic of each colored layer greatly controls the value of the final product.

In addition, for heat treatment encountered in the process of manufacturing a liquid crystal display device having a color filter, for example, for a sputtering process for providing a transparent electrode layer, and for light applied during use as a final product. It must have a high degree of resistance and must not impair certain optical properties. And of course, the dyes applied have good solubility in water (rate of dissolution and solubility),
It must be stable for a long time in an acidic dyeing bath.

Further, in the case of involving a step requiring fixing treatment, it is required that the fixing treatment effect is excellent. By the way, since protein type polymer substances such as gelatin, casein, and glue have a cationic group, they are dyed (colored) with a water-soluble anionic dye. When a photo-curable synthetic resin substrate is used instead of these, by retaining a cationic group in the resin component, it is dyed with a water-soluble anionic dye like a protein-based natural polymer substance. Become so.

As described above, the dyeing method has a feature that an extremely fine color pattern can be freely formed.
Since many manufacturing processes such as a photolithography process, a dyeing process, and a cleaning / fixing process are performed depending on the number of colors to be dyed, there is a high risk that yield may be reduced due to dust adhesion during manufacturing. Further, since the coloring density is almost proportional to the film thickness of the dyed resin film, the fluctuation of the film thickness causes unevenness of color and deteriorates the quality of the product. Depending on the order of dyeing, color unevenness may occur due to contamination or desorption of other colors. Further, a liquid crystal display device manufacturer has strongly demanded a method of reducing the number of steps for manufacturing a color filter to improve the yield and make the cost lower.

Recently, the inventors of the present invention formed a photosensitive resin thin film having a very high dyeability with an anionic dye on a transparent substrate and irradiating it with an energy ray to cure the thin film to form a cured film layer. Japanese Unexamined Patent Publication No. 7-77607 discloses a method for producing a color filter in which a dye solution is ejected at a predetermined position by an inkjet method to form a desired colored pattern with high density and accuracy.

[0011]

The conventional method for producing a color filter by the ink jet method has a problem in terms of density, and further improvement has been desired.

[0012]

The present inventors have completed the present invention as a result of various investigations for solving the above problems. That is, in the present invention, (1) an ink composition prepared by dissolving an anionic dye in an aqueous solution of an amide solvent is jetted onto a transparent substrate having a crosslinked layer of an anionic dye dyeable polymer by an inkjet method, A method for producing a color filter, which is characterized by performing water treatment after drying, (2) a method for producing a color filter according to the above (1) in which the amide solvent is a compound having no active hydrogen, and (3) using active hydrogen. Compounds not having are N-methylpyrrolidone, N, N-dimethylacetamide, N, N-dimerformamide,
N, N-diethylformamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,
3-dimethyl-2-imidazolidinone or N, N,
Any of the above (1) to (3), wherein the method for producing the color filter of (2) is N ′, N′-tetramethylurea, and (4) the concentration of the aqueous solution of the amide solvent is 3 to 40%. (5) The method for producing a color filter according to any one of (1) to (4) above, wherein the concentration of the anionic dye in the ink composition is 1 to 10%. 6) The method for producing a color filter according to any one of the above (1) to (5), wherein the ink composition does not substantially contain a solvent other than an amide solvent, and (7) an anionic dye-dyeable polymer. The method for producing a color filter according to any one of the above (1) to (6), which is a resin having a tertiary amino group, and (8) a crosslinked layer of an anionic dye-dyeable polymer is a pixel of a liquid crystal display device. Is patterned into a shape that corresponds to the shape of The method for producing a color filter according to any one of (1) to (7) above, and (9) the crosslinked layer of the anionic dye-dyeable polymer is patterned into a shape corresponding to the shape of the pixel of the liquid crystal display element. The method for producing a color filter according to any one of (1) to (8) above, wherein the black matrix is formed between the patterns, and (10) the water treatment is warm running water treatment. To (9) the manufacturing method of the color filter according to any one of (9), the temperature of water is 30 to 100 ° C.,
The method for producing a color filter according to any one of (1) to (10) above, wherein the pH of water is 3 to 7.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The color filter ink composition used in the present invention contains an amide solvent in addition to an anionic dye and water. The anionic dyes are used alone or as a mixture to prepare the ink, and the solvent of the ink is an aqueous solution of an amide solvent that can be mixed with water.
Examples of the amide solvent include N-methylpyrrolidone,
N, N-dimethylacetamide, N, N-dimerformamide, N, N-diethylformamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone or N,
A compound having no active hydrogen such as N, N ′, N′-tetramethylurea is preferable from the viewpoint of dyeing property, and N-methylpyrrolidone is particularly preferable. The content of the amide solvent in the ink composition is preferably 3 to 40% by weight, more preferably 5 to 25% by weight.

The dye concentration in the color filter ink composition used in the present invention is preferably 0.5 to 20% by weight, and particularly preferably 3 to 10% by weight. Inorganic salts such as sodium chloride and sodium sulfate are generally mixed in the anionic dye during the dye synthesis. Further, calcium ions, magnesium ions, etc. contained in general water are mixed in in a trace amount. These inorganic components not only significantly deteriorate the solubility and storage stability of the dye, but also cause corrosion and wear of the printer head, so it is desirable to remove these inorganic salts as much as possible.
In practice, standards have to be set and managed. Its content must be at least 1% by weight or less with respect to the anionic dye, but preferably 0.5% by weight or less,
It is more preferably 0.1% by weight or less. Further, in the color filter ink composition used in the present invention, a solvent other than an amide solvent such as an alcohol solvent from the viewpoint of dyeability, particularly a solvent other than an amide solvent having no active hydrogen is substantially used. Is preferably not included in. Here, “not substantially containing” means that a solvent other than an amide solvent, such as an amide solvent having no active hydrogen, is not contained in an amount such that the dyeing property is deteriorated.

The color filter ink composition used in the present invention may be produced, for example, as follows. That is, it is prepared by dissolving an anionic dye in an aqueous amide solvent solution, removing inorganic salts by a method such as ultrafiltration, reverse osmosis, or ion exchange, and then diluting or concentrating the dye to a desired dye concentration. To be done. The ink composition used in the present invention may contain a dye content of 0.5 to 20% by weight, and practically 3 to 10% by weight is preferable. After being prepared from such components, liquid filtration is performed using a cellulosic filter aid to remove dust, foreign substances, and other impurities, and then microfiltration is performed using a membrane filter (pore size 1 micron). It is preferable to perform microfiltration with a membrane filter having a pore size of 0.45 micron or less.

The ink composition used in the present invention, which is prepared by mixing as described above, is characterized in that it is particularly excellent in stability and long-term storability among various characteristics and does not clog the ejection orifice. It should be noted that stabilizers for the ink composition (sodium polyacrylate; for example, Kayakylator C-1000 manufactured by Nippon Kayaku Co., Ltd.) and antibacterial / antifungal agents (for example, Dell Top manufactured by Takeda Pharmaceutical Co., Ltd.) When adding, it is advisable to add it before the microfiltration.

Examples of the anionic dyes used in the ink composition include acid dyes, direct dyes and reactive dyes, and acid dyes are particularly preferable. Specifically, as the yellow dye, for example, CIAcid Yellow 3, ibid 17, ibid 38, ibid 40: 1, ibid 42, ibid 44: 1, ibid 49, ibid 6
1, 65, 67, 72, 79, 110, 1
14, the same 116, the same 117, the same 119, the same 121, the same 1
27, 129, 135, 141, 143, 1
55, ibid 158, ibid 161, ibid 194, ibid 204, ibid 2
07, 220, 232, 235, 241 and CI
Direct Yellow12, 86, 87, 130, 1
42, CIReactive Yellow 84, 102, and Nippon Kayaku Co., Ltd. color filter dye PC Yellow 42P
Examples of the orange dye include CIOr
ange10, ibid 19, ibid 33, ibid 50, ibid 56, ibid 67,
80, 108, 122, 142, 166, 130, CIDirect Orange 26, 39, CIReacti
ve Orange 1, 4 and the like.

As the red dye, for example, CI Acid Red
1, the same 6, the same 9, the same 14, the same 18, the same 35, the same 37, the same 42, the same 50, the same 52, the same 57, the same 73, the same 87, the same 8
8, same 89, same 92, same 97, same 106, same 111, same 114, same 118, same 128, same 134, same 138, same 143, same 143: 1, same 145, same 158, same 18
3, Same 186, Same 211, Same 214, Same 215, Same 21
7, ibid 219, ibid 225, ibid 226, ibid 249, ibid 25
4, the same 256, the same 257, the same 259, the same 260, the same 26
1, 263, 266, 274, 276, 27
8, ibid 289, ibid 299, ibid 301, ibid 303, ibid 30
7, ibid 315, ibid 316, ibid 317, ibid 336, ibid 33
7, ibid 341, ibid 355, ibid 357, ibid 359, ibid 36
2, ibid 366, ibid 383, ibid 399, ibid 405, ibid 40
7, 414, 416, 426, CIDirect Red
2, 23, 24, 31, 31, 39, 54, 7
9, ibid 83: 1, ibid 89, ibid 224, ibid 225, ibid 22
6, 227, 242, 243, CIReactive Red
5, 8 and 43, and Nippon Kayaku Co., Ltd. color filter dyes PC Red21P, PC Red136P, PC Red
137P, PC Magenta 10P, and the like, and examples of the purple dye include CI Acid Violet 21, 42, and 4
3, 47, 48, 49, 54, 97, 10
2 and the like.

As the blue dye, for example, CI Acid Blue
7, the same 9, the same 15, the same 22, the same 23, the same 25, the same 40,
Ibid 45, ibid 47, ibid 59, ibid 61: 1, ibid 62, ibid 7
8, the same 80, the same 83, the same 90, the same 104, the same 109, the same 112, the same 127, the same 127: 1, the same 129, the same 13
8, same 140, same 203, same 204, same 207, same 22
7, the same 228, the same 232, the same 247, the same 260, the same 26
4, 277, 278, 280, 283, 29
0, 333, 343, Direct Blue 106, 10
8 etc. and Nippon Kayaku Co., Ltd. color filter dye PC
Blue 43P, PCCyan 2P, and the like, and examples of the green dye include CIAcid Green 3, 5, 22, 22, 25, 27, 28, 41, etc., and Nippon Kayaku Co., Ltd.
Color filter dye PC GreenFOP, PC Green
100P etc. are mentioned.

As the black pigment, for example, CI Acid Black
1, 26, 31, 31, 48, 50, 52, 5
2: 1, 58, 60, 63: 2, 64, 10
7, Same 109, Same 110, Same 112, Same 113, Same 11
8, same 140, same 155, same 170, same 172, same 17
7, ibid 187, ibid 188, ibid 194, ibid 207, ibid 22
2, CIDirect Black17, the same 19, the same 22, the same 51,
62, 91, 112, 117, 118, 1
22, the same 132, the same 146, the same 154, the same 159, the same 1
69, 173, and the like.

Among these pigments, acid dyes and pigments for color filters are preferable. In addition, these dyes are used alone or as a mixture to form an ink, and when color unevenness is likely to occur in the mixture, it is preferable to use a dye having a single component structure. Examples of preferable dyes include the following dyes.

[0022]

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[0023]

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[0024]

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[0025]

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To carry out the method for manufacturing a color filter of the present invention, for example, the following may be carried out. That is, an anionic dye-dyeable polymer and a photosensitive compound containing an anionic dye-dyeable photosensitive compound as an essential component are dissolved in a solvent such as methyl cellosolve acetate, and the photosensitivity is determined by a method such as spin coating. The substrate is coated with the resin liquid, and the substrate is dried and then exposed to light to cure the photosensitive resin to obtain a photosensitive resin thin film (a crosslinked layer of an anionic dye-dyeable polymer).
The film thickness of the photosensitive resin thin film is preferably 0.2 to 5 μm, and particularly preferably 0.5 to 1.5 μm. The photosensitive resin thin film may be exposed with a predetermined pattern through a mask, or may be exposed by the whole surface without a pattern and cured. When the pattern is provided, partition walls may be formed as a black matrix in the gap between the patterns. The dyed thin film may be exposed through a mask to form a predetermined pattern, or may be exposed over the entire surface without a pattern.

The dyeing (coloring) by the ink jet method is
Either one color or multiple colors at the same time may be used. 70 ~ 180 ℃ after dyeing
Heat drying treatment is performed for 3 to 15 minutes on the hot plate or oven. Thereafter, water treatment is performed in order to sufficiently develop the dye printed on the dyed thin film. The water has a pH of 30 to 100 ° C, more preferably 60 to 80 ° C.
Those of 3 to 7 are used. For adjusting the pH of this water, organic acids, particularly lower carboxylic acids such as acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, tartaric acid and malic acid are preferably used. However, since it is not a fixing treatment, this water does not contain a fixing treatment agent such as tannin. The water treatment method is preferably dipping or shower treatment. Further, for the purpose of protecting the color filter layer after drying, a transparent protective layer is coated on the entire surface of the dyed thin film.

The printed matter of the dyed thin film made of the ink composition containing the anionic dye and the amide solvent used in the present invention is characterized in that the desorption of the dye during the above-mentioned water treatment is very small. The manufacturing method of the color filter is advantageous.

The substrate used in the present invention is not particularly limited as long as it is a colorless and transparent plate, and examples thereof include plates made of glass, polyester, polycarbonate, polyacrylate, polyether sulfone and the like. Its thickness is 0.5
About 1.5 mm is preferable.

The crosslinked product of the anionic dye-dyeable polymer used in the present invention is obtained by curing an anionic dye-dyeable photosensitive resin containing an anionic dye-dyeable polymer and a photosensitive compound as essential components. is there. The anionic dye dyeable polymer contains a hydrophilic monomer other than the anionic dye dyeable monomer and the anionic dye dyeable monomer (hereinafter simply referred to as “hydrophilic monomer”) as an essential component. This anionic dye dyeable polymer can be prepared by using a conventionally known solution polymerization method.

Here, the anionic dye dyeable monomer is
For example, it is a monomer having a tertiary nitrogen or a quaternary nitrogen in its molecule and has a property of imparting the dyeing ability of an anionic dye to the polymer. Specifically, for example, (N, N-dimethylamino) ethyl acrylate,
(N, N-dimethylamino) ethyl methacrylate,
(N, N-diethylamino) ethyl acrylate,
(N, N-diethylamino) ethyl methacrylate, 3
-(N, N-dimethylamino) propyl acrylate,
(N, N-di (C ₁ -C ₄ ) alkylamino) such as 3- (N, N-dimethylamino) propyl methacrylate
(C ₁ -C ₄ ) alkyl (meth) acrylate, 3-
(N, N-dimethylamino) propylacrylamide,
(N, N-di (C ₁ -C ₄ ) alkylamino) such as 3- (N, N-dimethylamino) propylmethacrylamide
(C ₁ -C ₄ ) alkyl (meth) acrylamide,
(N, N-diethylaminoethyl vinyl ether, 4-
Vinyl pyridine, diarylamine, 2-hydroxy-
3-methacryloyloxypropyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride are mentioned, but (meth) acrylamide-based monomers are preferable from the viewpoint of stability and the like, and in consideration of the dyeing property of anionic dyes, tertiary A monomer having nitrogen in its molecule, such as 3- (N, N
-Dimethylamino) propylacrylamide, 3-
A (meth) acrylamide-based monomer having a tertiary nitrogen in its molecule, such as (N, N-dimethylamino) propylmethacrylamide, is most preferable. These anionic dye dyeable monomers may be used alone or in admixture of two or more.

Examples of the hydrophilic monomer include hydroxy (C ₁ -C ₄ ) alkyl (meth), such as hydroxyethyl acrylate and hydroxyethyl methacrylate.
Examples thereof include acrylate, acrylamide, methacrylamide, dimethylaminoacrylamide, and methylaminoacrylamide, and (meth) acrylamide to which one or two (C ₁ -C ₄ ) alkyl groups may be bonded, vinylpyrrolidone, and the like. These hydrophilic monomers alone
Alternatively, two or more kinds are mixed and used.

The mixing ratio of these anionic dye dyeable monomer and hydrophilic monomer is such that the anionic dye dyeable monomer is 25 to 85% by weight, preferably 30 to 80% by weight, and the hydrophilic monomer is 15 to 75% by weight. , Preferably 20
~ 70% by weight is preferred.

Examples of the photosensitive compound include diazidochalcone, 4,4'-diazidostilbene-2,2'-disulfonic acid and 4,4'-diazidostilbene-2,2 '.
-Sodium disulfonate, 4,4'-diazidostilbene-2,2'-disulfonic acid (bis (methoxyethyl)) amide, 4,4'-diazidostilbene-2,
4,4′-diazidostilbene-2,2′-disulfonic acid (mono or bis ((C ₁ -C ₄ ) alkoxy (C) such as 2′-disulfonic acid (bis (ethoxyethyl)) amide)
₁ -C ₄₎ alkyl)) azide compounds such as amides, acrylic compound such as a known functional groups having two or more thereof. These photosensitive compounds may be used alone or in admixture of two or more. When an azide compound is used as the photosensitive compound, it is preferably used in an amount of about 2 to 15% by weight, more preferably 3 to 15% by weight based on the anionic dye-dyeable polymer.
It is preferable to use about 8% by weight.

In addition, 0.1 to 10 parts by weight of a compound having a (meth) acryloyl group other than the above-mentioned anionic dye dyeable monomer and hydrophilic monomer is added to 100 parts by weight of anionic dye dyeable polymer. In particular, the addition of about 0.5 to 6 parts by weight is preferable because the curing rate is increased. (Meta)
Examples of the compound having an acryloyl group include spiroglycol diacrylate [3,9-bis (2-acryloyloxy-1,1-dimethyl) 2,4,8,10-
Tetraoxaspiro [5,5] undecane] cyclohexane dimethylol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, neopentyl glycol di Acrylate, 1,4-
Butanediol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, bisphenol A epoxy acrylate, alkylene glycol diepoxy acrylate, glycidyl ester acrylate. , Polyester diacrylate, bisphenol A diacrylate,
Urethane-based diacrylate, methylenebisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, pentylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4- Examples thereof include butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.

When a conventionally known acrylic compound having two or more functional groups is used as the photosensitive compound, it is preferably used in an amount of about 10 to 40% by weight, more preferably 15 to 35% by weight based on the anion dye dyeable polymer. It is preferable to use about wt%. In this case, a photosensitizer may be used together.

When the strength of the photocured product of the anionic dye-dyeable polymer composed of the copolymer of the anionic dye-dyeable monomer and the hydrophilic monomer is insufficient, a hydrophobic monomer is used as a monomer constituting the polymer. When used together, its strength can be increased. Examples of the hydrophobic monomer include alkyl acrylates of (meth) acrylic acid such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, styrene and p-methylstyrene. Can be mentioned. The anionic dye dyeable monomer, the hydrophilic monomer, and the hydrophobic monomer are mixed in proportions of 20 to 70% by weight, preferably 25 to 60% by weight, and 10 to 60% by weight of the hydrophilic monomer. Preferably 2
It is preferable that the content is 0 to 50% by weight, the hydrophobic monomer is 10 to 50% by weight, and preferably 20 to 40% by weight. The molecular weight of the anionic dye-dyeable polymer thus prepared is preferably 5,000 to 200,000,
More preferably, it is about 10,000 to 100,000.

The anionic dye-dyeable photosensitive resin composition having the above composition is usually diluted with an organic solvent or the like before use. Examples of the organic solvent include methyl cellosolve, ethyl rososolve, tosopropyl cellosolve, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl ethyl ketone, methoxy isopropyl glycol, and the like. Dimethyl ether is preferred. These can be used alone or
Used as a mixture of more than one species. The proportion of the organic solvent in the photosensitive resin liquid varies depending on the composition in the resin liquid and cannot be unconditionally specified, but it is preferable that the resin liquid has a viscosity that can be applied to the surface of the substrate.
When an azide compound is used as the photosensitive compound, the water content in the photosensitive resin liquid is preferably 1% by weight or less in order to avoid its decomposition and side reactions.

As a specific example of the photosensitive resin composition, the photosensitive resin composition disclosed in JP-A-62-194203 is preferable. Examples of the photosensitive resin liquid include C
FR633DHP, CFR633L1 (all manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned. As the anionic dye-dyeable polymer, a resin having a tertiary amino group is preferable in terms of dyeability and heat resistance.

[0040]

EXAMPLES The present invention will be described in more detail below with reference to reference examples and examples. Reference example Preparation of anionic dye dyeable photosensitive resin liquid 3- (N, N-dimethylamino) propylacrylamide 38 parts 2-hydroxyethyl methacrylate 15 parts Dimethylaminoacrylamide 10 parts Vinylpyrrolidone 7 parts Methyl methacrylate 8 parts Methyl acrylate 22 parts The monomer of the above formulation was polymerized by a known solution polymerization method, and the polymer component was precipitated by pouring it into a large amount of isopropyl ether, and then the polymer (average molecular weight 90,000) was taken out and the water content was 1 w / w%. Dry until: 100 parts of this dry polymer were added to 2 parts of 4,4'-diazidochalcone and 4,4'-diazidostilbene-2,2 '.
-Disulfonic acid (bis (ethoxyethyl)) amide 6
Parts, silane coupler KBM603 (Shin-Etsu Chemical Co., Ltd.) 2 parts, isopropyl cellosolve 450 parts, and diethylene glycol dimethyl ether 450 parts are mixed and dissolved to obtain a photosensitive resin liquid having a water content of 1% by weight or less.

Example 1 Anionic dye dyeable polymer obtained by copolymerizing an anionic dye dyeable monomer, a hydrophilic monomer and a hydrophobic monomer and an azide compound dissolved in a solvent. CFR633DHP which is a light-sensitive resin liquid
100 parts (manufactured by Nippon Kayaku Co., Ltd.) and 0.05 parts of a silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. This is coated on a glass substrate by spin coating and dried at 110 ° C for 3 minutes, and then a belt conveyor type U
The entire surface is exposed through a V irradiator at an exposure amount of 150 mJ / cm ² and cured. The glass substrate having the thin film to be dyed (crosslinked layer of anionic dye-dystable polymer) thus formed is accurately positioned by an optical treatment method and set in an inkjet printer.

Then, the blue dye compound No. 15 copies,
A mixture of 20 parts of N-methylpyrrolidone and 75 parts of water is dissolved by heating, and a blue ink is prepared through a 0.2 μm membrane filter. Separately, green pigment compound N
o. 25 parts, N-methylpyrrolidone 20 parts, water 7
A mixture of 5 parts is heated and dissolved, and a green ink is prepared by passing through a 0.2 μm membrane filter. Further, red dye compound No. 35 parts, N-methylpyrrolidone 2
A mixture of 0 part and 75 parts of water was dissolved by heating to 0.2
Prepare a red ink through a μm membrane filter.

The above-mentioned blue ink is jetted by an ink jet to adhere to the portion to be colored blue of the thin film to be dyed. Next, the green ink described above is jetted onto the dyed thin film by an ink jet so that the dyed thin film is attached to the portion to be colored green. Finally, the above red ink is jetted onto the dyed thin film by an ink jet so that the dyed thin film is attached to a portion to be colored red. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, after showering the printed glass substrate with hot water at 70 ° C and pH 7 for 5 minutes, it is dried at 130 ° C for 10 minutes, and RG
・ B three color filters were obtained. Thus obtained,
The R, G, and B color filters each have a substantially circular pattern of about 150 μm, and have the same performance as a color filter formed by a conventional so-called dyeing method.

Example 2 Anionic dye dyeable polymer obtained by copolymerizing anionic dye dyeable monomer, hydrophilic monomer and hydrophobic monomer, azide compound and anionic dye dyeable monomer and hydrophilic monomer Other than CFR633L1 (manufactured by Nippon Kayaku Co., Ltd.), which is an anionic dye-staining photosensitive resin liquid in which a compound having a (meth) acryloyl group is dissolved in a solvent, and a silane coupling agent KBM60
3 (manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 0.05 part. This was coated on a glass substrate having a black stripe made of a pigment-dispersed resist by spin coating,
After drying at ℃ for 3 minutes, the entire glass surface is exposed and cured. Subsequently, the film is immersed in a 2% aqueous solution of tetramethyl hydroxide for development, washed with water, and dried at 150 ° C. for 20 minutes to obtain a highly dyeable resin film having a black stripe on the substrate (crosslinking of anionic dye dyeable polymer). Body layer). This glass substrate is precisely positioned and set in an inkjet printer.

Then, the yellow dye compound No. 42 copies,
A mixture of 10 parts of N-methylpyrrolidone and 88 parts of water is dissolved by heating and a yellow ink is prepared through a 0.2 μm membrane filter. Separately, magenta dye compound No. 52 parts, N-methylpyrrolidone 10 parts, water
A mixture of 88 parts is heated and dissolved, and a magenta ink is prepared by passing through a 0.2 μm membrane filter.
Further, cyan dye compound No. A mixture of 62 parts, 10 parts of N-methylpyrrolidone and 88 parts of water is dissolved by heating, and a cyan ink is prepared through a 0.2 μm membrane filter.

The above yellow ink is jetted by an ink jet to adhere to the portion to be colored yellow of the thin film to be dyed. Next, the above magenta ink is jetted onto the dyed thin film by an ink jet to adhere to the part of the dyed thin film to be colored magenta. Finally, the cyan ink is jetted onto the dyed thin film by an ink jet so that the dyed thin film is attached to a portion to be colored cyan. After this, heat drying and acetic acid 0.2% as in Example 1
Shower treatment was performed with hot water (pH about 3) at 70 ° C. containing Y, M, and C to obtain color filters of three colors.

Example 3 100 parts of CFR633L1 (manufactured by Nippon Kayaku Co., Ltd.) and a silane coupling agent KBM603 (Shin-Etsu Chemical Co., Ltd.)
(Manufactured) 0.05 parts. This was spin-coated on a glass substrate with a spinner to a film thickness of 1.5 μm, and
After drying at 0 ° C. for 20 minutes, exposure is performed using a mask and development is performed to form a stripe pattern having a line width of 20 μm and a line interval of 120 μm. The substrate having the stripe pattern thus obtained is accurately positioned and set in an inkjet printer. Then, the black pigment compound No. 7 6
Part, 20 parts of N-methylpyrrolidone, and 74 parts of water are dissolved by heating to prepare a black ink through a 0.2 μm membrane filter.

The above black ink is jetted by an ink jet to dye the stripe pattern in black. This is 150
Dry for 10 minutes at ℃ and then add 3 tannins to 1 liter of water.
g, tartarite 1 g, and acetic acid 3 g, soaked in a solution, fixed and dried. Subsequently, CFR633L1 is applied onto the substrate having the black stripes, and the same operation as in Example 2 is performed to obtain a color filter.

[0049]

EFFECT OF THE INVENTION The ink composition used in the present invention has a high solubility of the dye, is excellent in stability over time, and does not cause clogging of the inkjet printer head. This ink composition has the function of increasing the affinity of the dye for the highly dyeable photosensitive resin thin film used in the present invention and significantly reducing color bleeding. Therefore, a highly accurate colored pattern can be obtained. In particular, when the ink composition used in the present invention is combined with a resin having a tertiary amino group as an anionic dye-dyeable polymer, a color filter having a high concentration can be obtained only by water treatment without fixing treatment.
According to the present invention, it is not necessary to carry out the patterning and dye fixing treatment such as conventional dyeing three times, and the process is remarkably simplified. In addition, the decrease in yield due to dust adhesion in the conventional developing process and dyeing process is very small. Further, the control of the jetting position of the dye solution by the inkjet method is easy, and the accuracy can sufficiently meet the user's needs.

Claims (11)

[Claims] 1. An ink composition prepared by dissolving an anionic dye in an aqueous solution of an amide solvent is jetted onto a transparent substrate having a crosslinked layer of an anionic dye dyeable polymer by an inkjet method and dried, A method for producing a color filter, which comprises treating with water. 2. The method for producing a color filter according to claim 1, wherein the amide solvent is a compound having no active hydrogen. 3. A compound having no active hydrogen is N-methylpyrrolidone, N, N-dimethylacetamide, N, N-
Dimerformamide, N, N-diethylformamide,
N, N-dimethylpropionamide, N-methyl-ε-
The method for producing a color filter according to claim 2, wherein the color filter is caprolactam, 1,3-dimethyl-2-imidazolidinone or N, N, N ′, N′-tetramethylurea. 4. The concentration of an aqueous solution of an amide solvent is 3 to 40%.
4. The method for manufacturing a color filter according to claim 1, wherein 5. The method for producing a color filter according to claim 1, wherein the concentration of the anionic dye in the ink composition is 1 to 10%. 6. The method for producing a color filter according to claim 1, wherein the ink composition does not substantially contain a solvent other than an amide solvent. 7. The method for producing a color filter according to claim 1, wherein the anionic dye-dyeable polymer is a resin having a tertiary amino group. 8. The production of a color filter according to claim 1, wherein the crosslinked layer of the anionic dye-dyeable polymer is patterned in a shape corresponding to the shape of the pixel of the liquid crystal display element. Method. 9. The crosslinked layer of an anionic dye-dyeable polymer is patterned into a shape corresponding to the shape of a pixel of a liquid crystal display element, and a black matrix is formed between the patterns. 9. The method for manufacturing a color filter according to any one of items 8. 10. The method for producing a color filter according to claim 1, wherein the water treatment is a warm running water treatment. 11. The method for producing a color filter according to claim 1, wherein the temperature of water is 30 to 100 ° C. and the pH of water is 3 to 7.