WO1995002839A1

WO1995002839A1 - Method for manufacturing color filter

Info

Publication number: WO1995002839A1
Application number: PCT/JP1994/001163
Authority: WO
Inventors: Daisaku Matsunaga; Kenji Sawaki; Yoshifumi Saiki; Mariko Umeda
Original assignee: Nippon Kayaku Kabushiki Kaisha
Priority date: 1993-07-15
Filing date: 1994-07-15
Publication date: 1995-01-26
Also published as: GB2286063A; KR950703746A; SG43738A1; GB2286063B; GB9503696D0; CN1112376A

Abstract

A substrate is coated with a 0.6-νm-thick film of a photosensitive coloring resin, which exhibits a transmittance less than 5 % at the maximum absorption wavelength of the dye when it is immersed in a 4 % aqueous solution of a dye of more than 1,000 molecular weight for 15 minutes at room temperature or in a 0.2 % aqueous solution of a dye of more than 1,000 molecular weight for 10minutes at 60 °C. The resin film is hardened by exposure to energy rays, and then, a desired color pattern is formed on the film by applying a jet of aqueous dye, so that a color filter is provided.

Description

Description Color filter manufacturing method Technical field

The present invention relates to a method for manufacturing a color filter used for a liquid crystal display device or a solid-state imaging device.

Background art

Conventionally, in order to colorize a liquid crystal display device or a solid-state imaging device, a method of combining three primary color filters of red, green, blue, or yellow, magenta, and cyan has been adopted. I have. There are several methods for forming these color filters, but the most basic method is the so-called dyeing method. In this method, a transparent dyeable resin is formed in a mosaic form on a substrate, immersed in a dye bath, dyed, washed with water, and then subjected to a fixing treatment to form a dye-resistant film to form one color. This is repeated three times to form a color filter composed of fine color patterns of the three primary colors.

The dyeing method has the feature that extremely fine color patterns can be freely formed, but the number of photolithographic steps, dyeing steps, and washing steps depends on the number of colors to be dyed. Manufacturing processes such as the fixing process and the anti-dyeing process are many and complicated, and there is also a risk that the yield may be reduced due to adhesion of debris during manufacturing. Also, since the coloring concentration is almost proportional to the thickness of the dyed resin film, the variation in the film thickness causes uneven color and lowers the quality of the product. Depending on the order of staining, color unevenness due to contamination or detachment of other colors may occur. In addition, there is a strong demand from liquid crystal display element manufacturers for a method of reducing the number of color filter manufacturing steps, improving the yield, and making the filter more inexpensive.

Disclosure of the invention

The present inventors have conducted various studies to solve such a problem, and as a result, formed a photosensitive resin film having a specific dyeing property on a substrate, cured the cured resin film, and imprinted a photosensitive resin film on the cured photosensitive resin film. By jetting a predetermined dye solution to a predetermined position by the jetting method to form a desired coloring pattern, it has a coloring pattern with high density and high accuracy, and has heat resistance, chemical resistance, It has been found that a color filter excellent in light resistance and the like can be manufactured, and the present invention has been completed.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention

(1) A photosensitive resin thin film having the following dyeing properties (a) or (b) is formed on a substrate, and the thin film is cured by irradiation with energy rays. A method for producing a color filter, which comprises jetting a dye solution to a predetermined position by a jetting method to form a desired colored pattern;

(a) When a photosensitive resin thin film having a thickness of 0.6 is immersed in a 4% aqueous solution of a dye having a molecular weight of 100 or more at room temperature for 15 minutes at room temperature, the transmittance of the dye at the maximum absorption wavelength is 5%. % Is the following,

(b) When a photosensitive resin thin film having a thickness of 0.6 is immersed in a 0.2% aqueous solution of a dye having a molecular weight of 100 or more at 60 ° C for 10 minutes, the maximum absorption of the dye is obtained. The transmittance at the wavelength is 5% or less,

(2) The color filter according to (1), wherein the photosensitive resin thin film according to (1) is formed from a photosensitive resin composition containing an anion dye-dyeable polymer and a photosensitive compound. Manufacturing method,

(3) A polymer of a composition wherein the anion dye-dyeable polymer contains a tertiary nitrogen or quaternary nitrogen-containing anion dye-dyeable monomer, and a hydrophilic monomer other than the monomer. A method for producing the color filter according to (2) above,

(4) The anion dye-dyeable polymer is a tertiary nitrogen or a quaternary nitrogen-containing anion dye-dyeable monomer of 20 to 70% by weight.

The method for producing a color filter according to the above (2), which is a polymer of a composition comprising 10 to 60% by weight of a hydrophilic monomer other than the monomer and 10 to 50% by weight of a hydrophobic monomer,

(5) The color filter according to (4) above, wherein both the anionic dye-dyeable monomer having tertiary nitrogen or quaternary nitrogen and the hydrophobic monomer are (meth) acrylic monomers. Manufacturing method,

(6) The anionic dye-dyeable monomer is 3- (N, N-dimethylamino) propylamino or 3— (N, N-dimethylamino) propylmethacrylic Lua Mid (7) The method for producing a color filter according to the above (3) or (4), and (7) the anion dye-dyeable monomer is 3- (N, N-dimethylmethylamino) propyla Cryamide or 3 — (N, N-dimethylamino) propylmethacrylamide, which is a hydrophilic monomer other than the monomer 2 — Hydroxyshetti Lume acrylate, vinylpyrrolidone or dimethylamino acrylate, and the hydrophobic monomer is methyl methacrylate or methyl acrylate. A method for manufacturing the color filter of (4), which is a relay,

(8) The method for producing a color filter according to the above (2), wherein the water content in the resin solution in which the photosensitive resin composition is dissolved is lw / w% or less, and

(9) The method for producing a color filter according to the above (1), wherein a liquid in which a single component dye is dissolved in a solvent is used as the dye liquid.

About.

The method for manufacturing a color filter according to the present invention may be implemented, for example, as follows. That is, a highly dyeable photosensitive resin is dissolved in a solvent such as methyl solvent, and the photosensitive resin solution is coated on a substrate by a method such as spin coating, and dried. Exposure is performed by irradiation with energy rays such as ultraviolet rays to cure the photosensitive resin. When curing the photosensitive resin thin film, a predetermined pattern may be exposed through a mask, or the entire surface may be exposed and cured without providing a pattern, or a black mat may be used. The back exposure may be performed through a liquid. Pattern If a pattern is provided, a partition may be formed in the gap between the patterns as black matrix. The thickness of the photocured film obtained is usually about 0.3 to 2 m, preferably about 0.3 to 1.5 μm, and more preferably about 0.3 to lzm. When a black pigment is used, it is better to increase the film thickness. The photocured film thus obtained is heat-treated at a temperature of 100 ° C. (: up to 160 ° C., if necessary. The heat treatment time is not particularly limited, but is usually 15 to 50 minutes. The heat treatment may be performed by a known method using a hot plate or an oven, etc. Then, the heat treatment is performed at a predetermined position on the photosensitive resin thin film which is heat-treated or not heat-treated. The jet method applies a predetermined amount of the dye solution from room temperature to 70 '(: preferably at room temperature. The ink jet method ejects ink droplets from the nozzle. The dyeing (coloring) by this method may be carried out for each color or for multiple colors simultaneously Hot plate at 70 to 180 ° C after dyeing Alternatively, heat drying in an oven for 3 to 15 minutes will give a colorless letter. After that, if necessary, in order to prevent elution of the dye, it may be subjected to a fixing treatment in tannic acid and an aqueous solution of tartar and washed, and if necessary, For the purpose of protecting one color filter, a transparent protective layer may be coated on the entire surface of the dyed thin film.

The substrate used in the present invention is not particularly limited as long as it is a colorless and transparent plate. Examples of the substrate include glass, polyester, and polyester. Plates such as polycarbonate, polyacrylate, and polyethersulfone can be given. Its thickness is preferably about 0.5 to 1.5 mm.

As the high-dyeing photosensitive resin used in the present invention, (a) a photosensitive resin thin film having a thickness of 0.6 is added to a 4% aqueous solution of a dye having a molecular weight of 100 or more at room temperature. When immersed for 5 minutes, a dyeable photosensitive resin having a transmittance of 5% or less at the maximum absorption wavelength of the dye, or (b) a photosensitive resin thin film having a film thickness of 0.6 is converted to a molecular weight of 1 When immersed in a 0.2% aqueous solution of not less than 0.00 for 10 minutes at 60 ° C for 10 minutes, a dye-sensitive photosensitive resin having a transmittance of 5% or less at the maximum absorption wavelength of the dye is preferred. New Examples of the dye having a molecular weight of 1000 or more include PCGreen F0P (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the highly dyeable photosensitive resin satisfying the above conditions (a) or (b) include those containing anionic dye-dyeable polymer and a photosensitive compound as essential components. Is received. The anion dye-dyeable polymer is composed of an anion dye-dyeable monomer and a hydrophilic monomer other than the anion dye-dyeable monomer (hereinafter simply referred to as “hydrophilic monomer”). . The anion dye-dyeable polymer can be prepared by using a conventionally known solution polymerization method.

Here, the anion dye-dyeable monomer is, for example, a monomer having tertiary nitrogen or quaternary nitrogen in its molecule, and has a property of giving the polymer a dyeing ability of an anion dye. You It is something. Specifically, for example, (N, N—dimethylamino) ethyl creatate, (N, N—dimethylamino) ethyl methacrylate, (N, N—getylua) Mino) ethyl create, (N, N-getyla meth) methacrylate, 3-(N, N-dimethyl amino) propyl create, 3 - (N, N-di main Chirua Mi Roh) propyl meta click Li rate, etc. (N, N - di (C, ~ C ₄₎ Arukirua Mi Bruno) (C, ~ C ₄₎ alkyl (main evening 3) (N, N—dimethylamino), 3— (N, N—dimethylamino), propylate, creatine such as Mi-de (N, N - di (C, ~ ₍₄₎ Arukirua Mi Bruno) (C, ~ C ₄₎ alkyl (main evening) a click Li Amid, (N, N—Jetylamino) ethyl vinyl ether, 4—vinylpyridin, diarylamine, 2—hydroxyl 3—metacryloyloxyprobitory Metal ammonium chloride and metal chloride ammonium chloride can be cited, but from the viewpoint of stability and the like, (meta) acrylamide is used. Pd-based monomers are preferred, and in consideration of the dyeing properties of anion dyes in particular, 3 — (N, N-dimethylamino) propylene linoleamide, 3 — (N, N-dimethylamino) Propylmethacrylamide is most preferred, and these anionic dye-dyeable monomers are used alone or in combination of two or more.

Examples of the hydrophilic monomer include Hydroxy Shechi Le Ryo click Re les over preparative arsenide mud key Shechi zone les meta arsenate mud rk of data re les over preparative like (C, ~ C ₄₎ A Luki Le (meth) § grayed Re les over preparative, One or two (C) such as acrylonitrile mid, methacrylamid, dimethylamino acrylosol, methacrylaminoacrylamide , To (: ₄ ) may be (meth) acrylinoleamide, vinylpyrrolidone, etc. to which an alkyl group may be bonded, etc. These hydrophilic monomers may be used alone. Or two or more kinds are used in combination.

The proportion of the anionic dye-dyeable monomer to the hydrophilic monomer is from 25 to 85% by weight, preferably from 30 to 8% by weight. 0% by weight, 15 to 75% by weight of hydrophilic monomer, preferably 20 to 70% by weight o

Photosensitive compounds include, for example, diazidocalcone, 44'-diazidostilbene-1,2,2 * -disulfonic acid, 4,4'-diazidostilbene-1,2,2'-1 Sodium disulfonate, 4,4'-diazidostilbene 1,2,2 '-Disulfonic acid (bis (methoxethyl)) amide 4,4'-diazidostilbene 1-2 , 2'-, 4,4'-diazidostilbene-1,2,2,-, such as disulfonate (bis (ethoxystyl)) amide, -disulfonate (mono or bis ((C, ~ C ₄ ) Alkoxy (C) to C ₄ ) alkyl)) Amid compounds such as amides, and conventionally known acrylic compounds having two or more functional groups. . These photosensitive compounds may be used alone or in combination of two or more. It is. When an azide compound is used as the photosensitive compound, it is preferably used in an amount of about 2 to 15% by weight, particularly 3 to 8% by weight, based on the anionic dye-dyeable polymer. It is preferable to use it.

A compound having a (meth) acryloyl group other than the anion dye-dyeable monomer and the hydrophilic monomer is used as a dye-dyeable polymer. It is preferable to add 0.1 to 10 parts by weight, especially about 0.5 to 6 parts by weight with respect to 0 parts by weight, because the curing speed increases. Examples of the compound having a (meth) acryloyl group include, for example, spiroglycolate [3,9-bis (2—acryloyloxy 1,1 2,4,8,10 — Tetraoxaspiro [5,5] デ decane] cyclohexane dimethyl methyl crelate, ethylene Recall Refill Recall Recall Recall, Recall Recall Recall, Polyethylene Recall Relet, Boll Propylene glycol resin acrylate, butylene glycol resin acrylate, neopentyl glycol resin acrylate, 1,4, butanediol acrylate, 1, 6—Hexane diol diacrylate , Penta erythritol, solresia tallate, pentaerythritol, triacrylate, trimethylolpropane triacrylate, Novola Epoxy acrylate, bisphenol A epoxy acrylate, alkylene epoxy acrylate, glycidyl ester Acrylate, Polyester-based Jiacreate, Bisphenol A-based Jiacreate, Urethane-based Jiacreate, Methyl Lemon Attrino Reamide, Ethylene Glyco Remetriate, Diethylene Glyco Reagent Recreate, Triethylene Glyco No-registration evening create, Polyethylene registries Mesh Crate, Neopentyl Glycol Mesh Crate, 1,4-butane Gonore Regime Crate, 1,6—Hexane Gonore Regime Crate Rate, Trimethylol Prono. And creation rates.

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

If the strength of the photocured product of the anionic dye-dyeable polymer, which is a copolymer of an anionic dye-dyeable monomer and a hydrophilic monomer, is insufficient, the polymer may be used. When a hydrophobic monomer is used in combination as a monomer constituting the compound, the strength of the monomer can be increased. Examples of hydrophobic monomers include methyl acrylate, methyl methacrylate, ethyl butyl butyl acrylate, butyzo acrylate, and 2 — Alkyl esters of (meth) acrylic acid, such as ethylhexyl acrylate and 2-ethylethyl methacrylate Styrene, p-methyl styrene and the like. The proportion of the anion dye-dyeable monomer, hydrophilic monomer and hydrophobic monomer is preferably 20 to 70% by weight, preferably anion dye-dyeable monomer. 25 to 60% by weight, parenteral monomer 10 to 60% by weight, preferably 20 to 50% by weight, hydrophobic monomer 10 to 50% by weight Or 20 to 40% by weight. The molecular weight of the anion dye-dyeable polymer prepared in this manner is preferably 5,000 to 200,000, more preferably 1,000. 0, 0000 to 1 000 000.

The photosensitive resin composition having the above composition is usually used after being diluted with an organic solvent or the like. Examples of the organic solvent include methyl sorb, ethyl sorb, oxoxy, oxicellosolve, ethylene glycol monoethyl acetate, diethyl alcohol, ethylene glycol, diethyl alcohol, alcohol, and ethyl alcohol. Monoter, methyl ethyl ketone, methoxy isopropyl glycol, etc., but isopropoxy sol is preferred from the viewpoint of applicability, etc.Isolated propylene glycol dimethyl ether is preferred, or these may be used alone or in combination of two or more. Used as The proportion of the organic solvent in the photosensitive resin solution cannot be specified unconditionally because it varies depending on the composition in the resin solution, but the viscosity should be such that the resin solution can be applied to the substrate surface. It is preferred that When an azide compound is used as a photosensitive compound, its decomposition and side reactions are avoided. The water content in the photosensitive resin liquid is preferably 1 wZw% or less. Examples of the photosensitive resin liquid include CFR633DHP and CFR633L1 (both manufactured by Nippon Kayaku Co., Ltd.). ) And so on.

The anion dye is preferred as the dye used in the dye solution for ink jet. Examples of the anionic dye include an acidic dye, a direct dye, and a reactive dye. Specifically, as the yellow pigment, for example, CI Acid Yellow 3, 17: 38, 40: 1, 42, 44: 1, 49, 61, 61 6 5, 6 7, 7 2, 7 9 9, 11 10, 11 4, 11 6, 11 7, 11 9, 12 1, 12 7 , 129, 139, 143, 143, 155, 158, 161, 194, 204, 207 , 224, 232, 235, 241, CI Direct Yellow 12, 86, 87, 130, 134, CI Reactive Yellow 8 4, 102, etc., and dye PC for color filter manufactured by Nippon Kayaku Co., Ltd.

YeΠow 42 P and the like, and examples of orange color pigments include, for example, I. Orange 10, 19, 33, 50, 56, 67, and 67. 80, same 108, same 122, same 142, same 66, same 130, I. Direct Orange 26, same 39 I. Reactive Orange 1, same 4, etc. .

Examples of red pigments include CI Acid Red 1, 6, 9, 9, 14, 18, 35, 37, 42, 50, 52, 57, Same 73, Same 87, Same 88, Same 89, Same 9 2, 97, 10 6, 11 1, 11 4, 11 18, 12 28, 13 4, 13 8, 14 3, 14 3: 1, 145, 158, 183, 186, 221, 216, 215, 217, 219, same 2 25, 2 2 6, 2 4 9, 2 5 4, 2 5 6, 2 7 7, 2 5 9, 2 6 0, 2 6 1, 2 6 3, 2 266, 274, 276, 278, 289, 299, 310, 303, 307, 307, 315, same 3 16, 3 17, 3 3 6, 3 3 7, 3 4 1, 3 5 5, 3 5 7, 3 5 9, 3 6 2, 3 6 6, 3 383, 3939, 4105, 4107, 41.4, 41.6, 42.6, I. Direct Red 2, 23, 24, 3 1, 39, 54, 79, 83: 1, 89, 224, 225, 226, 227, 242, same 2 4 3, C I Reactive Red 5, 8 and 43, and Nippon Kayaku Co., Ltd. dyes for color filters PC Red 21 P, PC Red 13 P, PC Red 13 P , PC

Magenta 10P, etc., and examples of purple dyes include, for example, I. Acid Violet 21; 42, 43; 47; 48; 49; 49; 54; Examples of blue pigments include, for example, C. Acid Blue 7, 9, 9, 15, 22, 23, 23, 25, 40, and 40. 45, 47, 59, 61: 1: 1, 62, 78, 80, 83, 90, 104, 词 109, 111 2 and 1 2 7, 1 2 7: 1, 1 2 9, 1 3 8, 1 4 0, 2 3, 2 4 4, 2 7 7, 2 2 7, 2 2 8, Same 23, Same 24, Same 26, Same 26, Same 27, Same 28, Same 28, Same 28, Same 29, Same 33 , 343, CI Direct Blue 106, 108, etc., and Nippon Kayaku Co., Ltd. color filter dyes PC Blue 43P, PC Cyan 2P, etc. Examples of green pigments include I. Acid Green 3, 5, 22, 25, 27, 28, 41, and Nippon Kayaku Co., Ltd. Luster dyes PC GreenF OP, PC Green 100 P and the like.

Examples of black pigments include: I. Acid Black 1. 26, 31, 48, 50, 52, 52: 1, 58, 60, 63: 2, 64, 107, 109, 110, 110, 112, 113, 118, 140, 150, 55, 170 1 7 2 1 7 7, 1 8 7, 1 8 8, 1 9 4, 2 7 7 2 2 2, CI Direct Black 17, 19, 2 2 5, 6 2, 9 1 1 1 1 2, 1 1 1 7, 1 1 8 1 2 2, 1 3 2, 1 4 6, 1 5 4, 1 5 9, 1 6 9, Same as 17.3.

Of these dyes, acid dyes and dyes for color filters are preferred. These dyes may be used alone or as a mixture to make an ink. If the mixture tends to cause color unevenness, a single component dye may be used alone. Is preferred. As the solvent for the ink, water or an organic solvent aqueous solution that can be mixed with water is used. Organic solvents include methyl alcohol, ethyl alcohol, butyl alcohol, methylcellosolve, ethylcellosolve, ethyl alcohol, and ethyl glycol. One-hole, diethylene glycol monomethyl ether, diethylene glycol monoether ether, dimethyl methyl amide, dimethyl methyl amide, N-methyl Chill-pigs, etc. are available. The dye concentration in the ink is preferably 0.5 to 20%, and particularly preferably 3 to 10%. If necessary, the color ligating solution may be used after being filtered using a membrane filter or the like.

Hereinafter, the present invention will be specifically described with reference examples and examples.

Reference Example Preparation of Dyeable Photosensitive Resin Solution Used in the Present Invention 3-(N, N-dimethylamino) propylacrylamide 38 8 parts

2 — Hydroxyl methyl methacrylate 1 5 dimethyl dimethyl amino chlorinated amide 10 0 vinyl pyrrolidone 7 dimethyl methacrylate 8 dimethyl methacrylate 2 2 parts Monomer of the above formulation is polymerized by a known solution polymerization method, and poured into a large amount of isopropyl ether to precipitate a polymer, and then the polymer (average molecular weight 9 0 0 0) and remove it to a water content of 1 wZw% or less. To the dried polymer 100 parts, 4 parts, 4 parts of dicarboxylic acid, 2 parts, 4,4 parts of diazide stilbene —2,2'-disulfonic acid (bis (eth 6) Amid 6 parts, silane coupler KBM 603 (Shin-Etsu Chemical Co., Ltd.) 2 parts Isoproboxise mouth solve 450 parts, diethyl glycol 450 parts of tyl ether is mixed and dissolved to obtain a dyeable photosensitive resin solution having a water content of 1 wZw% or less.

Example 1

Solvents are obtained by copolymerizing anionic dye-dyeable monomers, hydrophilic monomers and water-hydrophobic monomers, and dye-polymerizable dyes and azide compounds as solvents. 100 parts of CFR 633 DHP (manufactured by Nippon Kayaku Co., Ltd.) and a silane coupling agent KB 603 (Shin-Etsu Chemical) (Industrial Co., Ltd.) Mix 0.05 parts. This was coated on a glass plate by the spin coating method, dried at 110 ° C for 3 minutes, passed through a belt conveyor UV irradiator, and exposed to a light of about 15 Expose the entire surface at 0 mJ / cm ² and cure. The cured film has a thickness of 0.6 m. When dyed by the method (a) using PC Green FP, a dye having a molecular weight of 100 or more, the maximum absorption wavelength ( The transmittance at 660 nm) is 0.2% or less. The glass substrate having the thin film to be dyed thus formed is accurately positioned by an optical processing method, and set in an ink jet screen. 4% aqueous solution of PC Blue 43P (color pigment for Nippon Kayaku Co., Ltd.) Is sprayed with an ink jet as a dye solution through a 0.2 membrane lamp and attached to a portion of the thin film to be dyed to be colored blue. Next, a 0.2% aqueous membrane solution of PC GreenF0P (a color filter for Nippon Kayaku Co., Ltd.) is passed through the membrane filter. The dye solution is sprayed with an ink jet to adhere to a portion of the dyed thin film to be colored green. Finally, a 0.2% membranum solution of PC Red 21 P (a color filter for Nippon Kayaku Co., Ltd., color filter) of 4% methyl sorbent solution was added to the dyed thin film. The dyed liquid is jetted through a filter as an ink jet with an ink jet, and adheres to the portion of the dyed thin film to be colored red. This is heated and dried on a hot plate heated to 150 ° C for 10 minutes. Next, as a dye fixing treatment, the stained glass substrate is immersed in a solution containing 3 g of tannin, 1 g of tartar, and 3 g of acetic acid in 1 liter of water, and the mixture is kept at 70 ° C for 7 minutes. After the treatment, wash with water and dry at 130 ° C for 10 minutes to obtain a color filter of R, G, B colors. The R, G, and B three-color color filters each have a roughly square pattern of about 150 m each, and a color filter formed by a conventional so-called dyeing method. It has equivalent performance.

Example 2

Anion dye-dyeable monomers, hydrophilic monomers and water-hydrophobic monomers are copolymerized to obtain anion dye-dyeable polymers, azide compounds, and dyeable dyes. mono CFR 63 3 L which is a resin solution of a dyeable photosensitive resin composition type in which a compound having a (meth) acryloyl group other than a monomer and a hydrophilic monomer is dissolved in a solvent. 1 100 parts (Nippon Kayaku Co., Ltd.) and 0.05 parts of silane coupling agent KBM603 (Shin-Etsu Chemical Co., Ltd.) are mixed. This is coated on a glass substrate having a black stripe made of a pigment dispersion resist by the spin coating method, dried at 110 for 3 minutes, and then dried from the glass surface. The entire surface is exposed and cured. Then, immerse in 2% tetramethyl thiol hydroxide aqueous solution, develop, wash with water, dry at 150 ° C for 20 minutes, and perform high staining with black stripe on substrate. Obtain a conductive resin film. The thickness of this cured film is 0.6 m, and when dyed by the method (b) above using PC GreenF0P which is a dye having a molecular weight of 100 or more, its maximum absorption wavelength (66 0 nm) is 0.4% or less.

This glass substrate is set on an ink jet printer. A 2% aqueous solution of PC Magenta 41P (color pigment for Nippon Kayaku Co., Ltd.) is passed through a 0.2 / m membrane filter to obtain a dye solution. The thin film to be dyed is sprayed with a jet to adhere to a portion of the thin film to be dyed which is to be colored magenta. Next, a 2% aqueous solution of PC Yellow 42P (a color filter dye manufactured by Nippon Kayaku Co., Ltd.) was passed through the 0.2 m membrane filter through the dyed thin film. It is sprayed with an ink jet as a dye solution, and adheres to the portion of the dyed thin film to be colored yellow. Finally, on this dyed thin film, A 2% aqueous solution of PC Cyan 2P (a colorant for color filters made by Nippon Kayaku Co., Ltd.) is passed through a 0.2 μm membrane filter to form a dye solution, which is then ink. It is jetted and attached to the area to be colored cyan. Thereafter, heat drying and dye fixing treatment were carried out in the same manner as in Example 1 to obtain a Y, M, and C three-colored color filter.

Example 3

Mix 100 parts of CFR 633 L1 (Nippon Kayaku Co., Ltd.) with 0.05 parts of silane coupling agent KBM603 (Shin-Etsu Chemical Co., Ltd.) . This was spin-coated on a glass substrate to a thickness of 1 with a spinner, dried at 90 for 20 minutes, exposed using a mask, developed, and developed to a line width of 20 Atm and a line width of 20 Atm. Stripno, with a spacing of 120 A £ m. Form a turn. The substrate having the stripe pattern obtained in this way is precisely positioned and set on an ink jet printer. A 4% aqueous solution of PC black 181P (a color filter for Nippon Kayaku Co., Ltd.) for coloring is passed through a 0.2 / m membrane filter to form a dye solution. Spray with an ink jet to stain the stripe pattern black. This is dried at 150 ° C for 10 minutes, then immersed in a solution containing 3 g of tannin, 1 g of tartar and 3 g of acetic acid in 1 liter of water, fixed and dried. . Subsequently, CFR6333L1 is applied on the substrate having the black stripe, and the same operation as in Example 2 is performed to obtain a color filter. Industrial applicability

According to the present invention, it is not necessary to perform patterning and dyeing fixation treatments three times each as in conventional dyeing, and the process is significantly simplified. In addition, the yield decrease due to the adhesion of rubbing in the conventional developing and dyeing processes is very small. In addition, the control of the jetting position of the dye solution by the ink jet method is easy, and the accuracy can sufficiently meet the needs of the user. The highly dyeable photosensitive resin thin film used in the present invention has an extremely high affinity for dyes and very little color bleeding. Therefore, a power filter having a coloring pattern with high density and high accuracy can be obtained. Further, according to the method of the present invention, a color filter having good heat resistance, chemical resistance, light resistance and color characteristics can be obtained.

Claims

The scope of the claims

1. A photosensitive resin thin film having the following dyeing properties (a) or (b) is formed on a substrate, and the thin film is cured by irradiating it with an energy ray. A method for producing a color filter, which comprises forming a desired colored pattern by jetting a dye solution to a predetermined position by a jet method.

(a) When a photosensitive resin thin film having a thickness of 0.6 is immersed in a 4% aqueous solution of a dye having a molecular weight of 100 or more at room temperature for 15 minutes at room temperature, the transmittance of the dye at the maximum absorption wavelength is 5%. % Or less.

(b) When the photosensitive resin thin film having a thickness of 0.6 / is immersed in a 0.2% aqueous solution of a dye having a molecular weight of 100 or more at 60 ° C for 10 minutes, The transmittance at the maximum absorption wavelength is 5% or less.

2. The color filter according to claim 1, wherein the photosensitive resin thin film according to claim 1 is formed of a photosensitive resin composition containing an anion dye-dyeable polymer and a photosensitive compound. Construction method.

3. The anion dye-dyeable polymer is a polymer of a composition containing an anion dye-dyeable monomer having a tertiary nitrogen or a quaternary nitrogen, and a hydrophilic monomer other than the monomer. Item 2. A method for manufacturing a color filter according to item 2.

4. The anion dye-dyeable polymer is tertiary nitrogen or Anionic dye-dyeable monomer having quaternary nitrogen 20 to 70 weight, hydrophilic monomer other than the monomer 10 to 60% by weight, and hydrophobic monomer 10 The method for producing a color filter according to claim 2, which is a polymer having a composition of from 50 to 50% by weight.

5. The anion dye-dyeable monomer having tertiary nitrogen or quaternary nitrogen and the hydrophobic monomer are both (meta) -terminated acryl-based monomers. This is the color filter production method.

6. When the anionic dye-dyeable monomer is 3 — (N, N — dimethylamino) propylene linoleamide or 3 — (N,

The method for producing a color filter according to claim 3 or 4, wherein the method is N-dimethylamino) propylmethacrylorea amide.

7. When the anionic dye-dyeable monomer is 3- (N, N-dimethylamino) propyl amide or 3— (N, N-dimethylamino) propyl methacrylate A hydrophilic monomer other than the monomer is 2—hydroxylmethacrylate, vinylpyrrolidone or dimethylaminoacrylamide; and a hydrophobic monomer. 5. The method for producing a force filter as claimed in claim 4, wherein the functional monomer is methyl methacrylate or methyl acrylate.

8. The method for producing a color filter according to claim 2, wherein the water content in the resin solution in which the photosensitive resin composition is dissolved is 1 or less.

9. The colorant according to claim 1, wherein a single component dye is dissolved in a solvent as the dye solution. Filter manufacturing method.