JPH0943413A - Color filter and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter having excellent workability, productivity, heat resistance and chemical resistance, and to provide its production method. SOLUTION: This color filter consists of a substrate and color layers formed by using color compsns. each comprising an unsatd. group-contg. polyamide imide resin, org. dye, dispersant and polyfunctional unsatd. compd. for each color and forming a desired pattern for each color to form a color layer of each color. The color compsn. above described is applied by coating or printing on a substrate, exposed to light and then hardened to form a color layer.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention can provide a suitable color filter by providing it in a liquid crystal cell of a color liquid crystal display device, and more specifically, it is a TN (twisted nematic) type, STN (super twisted) type.・
Nematic) type, GH (guest host) type and FLC
The present invention relates to a color filter for color separation suitable for a (ferroelectric liquid crystal) type liquid crystal display device and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, color filters are manufactured by a dyeing method, a pigment method or the like. However, since the dyeing method uses natural organic substances such as gelatin and casein, the heat resistance is poor and the weather resistance of the dye is poor. In the pigment method, it is difficult to make a practical color filter because the pigment method disperses the pigment uniformly and there is no binder having excellent heat resistance. Regarding the heat resistance, vapor deposition of a transparent electrode for operating the liquid crystal on the color filter, coating of a polyimide resin for orienting the liquid crystal, and baking are performed, and a material that withstands this is required. On the other hand, when it is used for outdoor and on-vehicle use, the weather resistance may directly receive sunlight, and high weather resistance has been desired.

[0003]

SUMMARY OF THE INVENTION In view of the above problems of the prior art, the object of the present invention is to provide a color filter having excellent heat resistance, weather resistance and chemical resistance, and to disperse dyes and dyes. It is to provide a color filter having good light transmittance.

[0004]

In order to achieve the above object, the gist of the present invention is to provide a polyamideimide resin containing trimellitic anhydride and dicyclohexylmethane diisocyanate and / or isophorone diisocyanate on a substrate with a carboxyl group, Polyamideimide resin containing an unsaturated group obtained by copolymerizing and / or modifying an unsaturated compound containing at least one selected from a hydroxyl group, an epoxy group and an amino group, an organic dye, a dispersant and a polyfunctional unsaturated compound. The coloring composition containing the main component is coated or printed, exposed and cured, and optionally developed to form a colored layer. Hereinafter, the present invention will be described in more detail.

The polyamide-imide resin used in the present invention comprises an acid component and a diisocyanate (amine) component,
It can be synthesized in a polar solvent having a high boiling point by a usual method such as an isocyanate method or an acid chloride method.

Trimellitic acid is indispensable as an acid component used in the synthesis of the polyamide-imide used in the present invention, and a part of it should be replaced with a polyvalent carboxylic acid, acid chloride or acid anhydride shown below. Can be done. However, it is not limited to these. As the acid anhydride, ethylene glycol bisanhydrotrimellitate, propylene glycol bisanhydrotrimellitate, 1,
4 butanediol bisanhydrotrimellitate, hexamethylene glycol bisanhydrotrimellitate,
Alkylene glycol bis-anhydro trimellitates such as polyethylene glycol bis-anhydro trimellitate and polypropylene glycol bis-anhydro trimellitate, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride 3, 3 ', 4, 4' Examples thereof include diphenyl sulfone tetracarboxylic acid anhydride, 3,3′4,4 ′ diphenyl tetracarboxylic acid anhydride and 4,4 ′ oxyphthalic acid anhydride.

As the polycarboxylic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid,
4,4 ′ biphenyl dicarboxylic acid, 4,4 ′ biphenyl ether dicarboxylic acid, 4,4 ′ benzophenone dicarboxylic acid, pyromellitic acid 3, 3 ′, 4, 4 ′ benzophenone tetracarboxylic acid 3, 3 ′, 4, 4'biphenylsulfone tetracarboxylic acid, 3,3 ', 4,4' biphenyl tetracarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, azelaic acid, stilbene dicarboxylic acid, etc. Examples thereof include acid chlorides of the above-mentioned polycarboxylic acids. Among these polyvalent carboxylic acids, cyclohexanedicarboxylic acid is preferable from the viewpoints of transparency, solvent solubility, heat resistance, and polymerizability, and the copolymerization ratio thereof is 1 for trimellitic anhydride.
It should be 0 mol% or more, preferably 20 mol% or more.
When the copolymerization ratio of trimellitic anhydride is 10 mol% or less, heat resistance and solubility are deteriorated, which is not preferable.

As the isocyanate component, dicyclohexylmethane 4,4'diisocyanate, 1,3
Bis (isocyanatomethyl) cyclohexane, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, diphenylmethane 4,4 'diisocyanate,
3,3 'dimethyldiphenylmethane 4, 4'diisocyanate 3, 3'diethyldiphenylmethane 4, 4'diisocyanate 3, 3'dichlorodiphenylmethane 4, 4'diisocyanate, 4, 4'diisocyanate 3, 3'dimethylbiphenyl, hexa Examples thereof include methylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate and m-phenylene diisocyanate. Among these isocyanate components, dicyclohexylmethane 4,4 ′ diisocyanate and / or isophorone diisocyanate are preferable in terms of transparency, solubility and heat resistance.

As the amine component, 4,4'-diaminodicyclohexylmethane, 1,3 cyclohexanebis (methylamine), o-chloro p-phenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4 '. Diaminodiphenyl ether, 4,4'diaminodiphenylmethane, 4,4'diaminodiphenyl sulfone, 3,4 diaminodiphenyl sulfone, 4,
4'diaminobenzophenone, 3,4 diaminobenzophenone, 2,2'bis (aminophenyl) propane,
2,4 tolylenediamine, 2,6 tolylenediamine, p
-Xylylenediamine, m-xylylenediamine, isophoronediamine, hexamethylenediamine and the like.

The polyamideimide resin of the present invention has an inherent viscosity of 0.05 dl / g or more, preferably 0.1 dl / g or more. When the logarithmic viscosity is 0.05 or less, the coating film is fragile and easily peeled off from the glass substrate.

Solvents used in the synthesis of the polyamideimide resin of the present invention include amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2pyrrolidone and dimethylimidazolidinone, nitro solvents such as nitrobenzene and dimethylurea. Examples of the solvent include urea-based solvents, sulfur-based solvents such as dimethyl sulfoxide, ester-based solvents such as γ-butyrolactone, and dimethyl imidazolidinone and / or γ-butyrolactone are preferable because they have few side reactions and are less colored.

The polyamideimide of the present invention is
It is synthesized by stirring at 50 to 230 ° C., preferably 80 to 200 ° C., but in order to accelerate the reaction, amines such as triethylamine, lutidine, picolinetriethyldiamine, lithium methylate, sodium methylate, sodium ethylate, etc. Alkali metal, alkaline earth metal compound or cobalt, tin, such as lath, potassium butoxide, potassium fluoride, sodium fluoride,
It may be carried out in the presence of a metal such as zinc or a catalyst such as a semi-gold compound.

The method for introducing an unsaturated group into the polyamideimide resin of the present invention may be carried out during the above-mentioned polymerization or after the completion of the polymerization. Further, the unsaturated group can be introduced into the molecular skeleton of polyamideimide or can be introduced into the terminal.

The unsaturated compound used in the present invention is not particularly limited, but an unsaturated compound having a functional group such as a hydroxyl group, a carboxyl group, an epoxy group and an acid anhydride group is preferable, and specifically, maleic acid, Maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, glycidyl methacrylate, hydroxyethyl methacrylic acid, glycerin monoacrylate, glycerin diacrylate, trimethylolpropane monoacrylate, trimethylolpropane diacrylate, pentaerythritol monoacrylate, Examples thereof include pentaerythritol diacrylate and pentaerythritol triacrylate.

The reaction for introducing an unsaturated group is usually 50 to 230.
C., preferably 150.degree. C. or lower, and a radical polymerization inhibitor of an unsaturated compound may be used if necessary.
As the polymerization inhibitor, p-benzoquinone, naphthoquinone, phenanthraquinone, p-xyloquinane, p-toluquinone, 2,6 dichloroquinone, 2,5 diphenyl-
quinones such as p-benzoquinone, 2,5 diacetoxy-p-benzoquinone, hydroquinone, hydroquinones such as pt-butylcatechol, 2,5-di-t-butylhydroquinone, di-t-butylparacresol, hydro Phenols such as quinomonomethyl ether, acetamidine acetate, acetamidine acetate, acetamidine sulfate, nadnoamidines, phenylazine, hydrazines such as hydrazine hydrochloride, trimethylbenzyl ammonium chloride, lauryl pyridinium chloride, trimethylbenzyl ammonium oxa Examples thereof include quaternary ammonium salts such as rate, thiazines such as phenothiazine, oximes such as quinone dioxime and cyclohexanone oxime, but are not limited to these. Not. Further, these polymerization inhibitors can be used alone or in a mixed system of two or more kinds.

The unsaturated group-containing polyamideimide resin solution thus synthesized can be used as it is, but it is used as a solution in which the powder obtained by introducing the polymerization solution into the coagulation bath is redissolved. You can also The powder is not only soluble in amide solvents such as dimethylformamide, dimethylacetamide, N-methyl-2pyrrolidone,
General alcohol, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t
ert butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol and other monovalent aliphatic alcohols, ethylene glycol,
Examples include polyhydric alcohols such as propylene glycol, trimethylolpropane, glycerin, and pentaerythritol, aromatic alcohols such as benzyl alcohol, and low boiling point alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol due to the drying property of the coating film. preferable.

Further, a solvent other than alcohol can be mixed and used. As the solvent other than alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexano, methyl acetate, ethyl acetate, ester solvents such as cellosolve acetate,
Examples of the solvent include hydrocarbon solvents such as benzene, toluene, xylene and solvesso, ether solvents such as tetrahydrofuran, 1,4 dioxane and diglyme, and toluene and tetrahydrofuran are preferable from the viewpoint of solubility and drying property of the coating film.

Next, a color filter using an unsaturated group-containing polyamideimide resin and a method for producing the same will be described. The structure of the color filter is generally a red filter (R), a green filter (G), and a blue filter (B) on a transparent substrate made of glass or transparent resin.
Further, a black or opaque light shielding layer is formed, and a transparent electrode layer is further formed on the color filter. Each filter is composed of an unsaturated group-containing polyamideimide resin, a pigment, a dispersant, and a coloring composition containing a polyfunctional unsaturated compound as a main component.

Since the pigment plays a role of decomposing white light, it must have excellent transparency, light resistance and heat resistance.
The particle size of the pigment needs to be smaller than the wavelength of visible light, and is 0.3 μm or less, preferably 0.1 μm or less, and an organic pigment is particularly desirable. The dispersant is necessary for uniformly dispersing the pigment in the polyamide-imide resin, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, etc. are used.

The mixing ratio of the pigment to 100 parts of the polyamide-imide resin is usually 20 to 40 parts, preferably 25 to 3 parts.
It is 0 part, and when the ratio of the pigment is small, the optical density decreases,
On the other hand, if it is too large, the dispersibility and the coatability are deteriorated. The dispersant to pigment ratio is preferably 0.02 to 0.1, but is not particularly limited to this range.

The polyfunctional unsaturated compound is added in order to effectively crosslink the unsaturated group-containing polyamideimide resin of the present invention and to further improve heat resistance and chemical resistance. Specifically, ethylene glycol diacrylate, propylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, glycerin diacrylate, glycerin triacrylate, trimethylol propane diacrylate,
Examples thereof include, but are not limited to, trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol toluacrylate, pentaerythritol tetraacrylate, and polyfunctional epoxy acrylate, alone or in a mixture of two or more. The blending amount of the polyfunctional unsaturated compound varies depending on the type, but is usually 10 to 200 parts, preferably 20 to 1 part with respect to 100 parts of the unsaturated group-containing polyamideimide.
00 parts. When the compounding amount of the polyfunctional unsaturated compound is 10 parts or less, the crosslinking is insufficient and the chemical resistance to N-methyl-2-pyrrolidone, dimethylacetamide and the like deteriorates, and when it is 200 parts or more, the heat resistance decreases.

When a composition or the like is prepared according to the present invention, an unsaturated group-containing polyamideimide resin, an organic dye, a dispersant, a polyfunctional unsaturated compound and the like are dispersed in a roll mill, a ball mill, a sand mill or an attritor. Disperse and mix with a kneader.

The method for producing a color filter of the present invention comprises:
A step of forming a varnish of the coloring composition as described above, a step of adding a radical initiator and / or a photopolymerization initiator,
Apply the obtained colored varnish to a transparent substrate with a spinner or a roll coater or print it in a pattern beforehand and dry it.The step of forming a pattern by etching with an alcohol solvent after partial exposure through a mask is blue. , Green and red, and a black coloring composition is applied between the color layers, followed by back exposure to form black stripes or lattices.

[0024]

The present invention will be described in more detail with reference to the following examples. Example 1 (Production of Polyamideimide Resin Containing Unsaturated Group) 0.5 mol of trimellitic anhydride, 0.5 mol of cyclohexanedicarboxylic acid and 1 of isophorone diisocyanate were placed in a reaction vessel.
Mol to a concentration of 5 with dimethyl imidazolidinone as a polymerization solvent.
The mixture was charged to 0% by weight, heated to 150 ° C. and reacted for 5 hours, then, while cooling to 100 ° C., 0.3 mol of glycidyl methacrylate and dimethylimidazolidinone were added to adjust the concentration to 30% by weight. The reaction was continued for 3 hours. The obtained polymer solution was cooled to room temperature, poured into a large amount of water to coagulate, sufficiently washed with water, and then dried to obtain a powder. The unsaturated group-containing polyamideimide resin has an inherent viscosity of 0.3 dl / g and a glass transition temperature of 245 ° C.
Met.

(Production of Color Filter) The unsaturated group-containing polyamideimide resin synthesized in Example 1 was mixed at a concentration of 10
To a solution of 90.1 g of a solution of toluene and ethanol in a mixed amount of 9% and 9% of a pigment, 0.9 g of a pigment and 0.9 g of a dispersant are added and kneaded with a three-roll mill to disperse the red, green and blue varnishes. It was created. To 100 g of each colored resin, 3 g of hydroxyethyl acrylate, 1 g of pentaerythritol tetraacrylate and 0.
5 g was added and stirred to obtain a uniform coloring composition. The blue composition was spin-coated on a substrate and dried. 1500mJ / using a mask of pixel size 30μ × 100μ
It was exposed with a light amount of cm ² and developed in an equal amount mixed solvent of ethanol / toluene, and the pigment adhering to the substrate was wiped off and dried. For each of green and red, each composition was similarly fixed to complete a color filter.

The resulting color filter was immersed in N-methyl-2-pyrrolidone, γ-butyrolactone and dimethylacetamide for 30 minutes at 40 ° C., and the appearance of the pattern was observed with a microscope, but no abnormalities such as peeling were observed. In addition, after being immersed in the above solvent and heat-treated at 250 ° C. for 1 hour, there was no change in hue.

[0027]

As described above, a color filter having excellent chemical resistance and heat resistance can be obtained by photocuring an unsaturated group-containing polyamideimide resin and a polyfunctional unsaturated compound in combination. It is extremely useful in practice due to its excellent productivity and productivity.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroki Yamaguchi Inventor Hiroki 2-1-1 Katata, Otsu City, Shiga Toyobo Co., Ltd. (72) Inventor Masanori Kobayashi 2-1-1 Katata, Otsu, Shiga Prefecture Toyobo Co., Ltd. Research Institute (72) Inventor Shigeru Yoneda 1-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Research Institute

Claims (4)

[Claims] 1. A coloring composition containing a polyamideimide resin having an unsaturated group, an organic dye, a dispersant, and a polyfunctional unsaturated compound as a main component is used on a substrate, and a desired pattern shape is formed with an arbitrary number of colors. A color filter comprising a colored layer for each color. 2. A polyamideimide resin containing an unsaturated group is a polyamideimide resin containing trimellitic anhydride and dicyclohexylmethane diisocyanate and / or isophorone diisocyanate, and a carboxyl group,
At least 1 selected from hydroxyl group, epoxy group and amino group
The color filter according to claim 1, wherein an unsaturated compound containing a seed is copolymerized and / or modified. 3. A coloring composition containing a polyamideimide resin having an unsaturated group, an organic dye, a dispersant and a polyfunctional unsaturated compound as a main component is coated on a substrate, and a desired composition is obtained by a partial exposure and development process. The colored layer is repeatedly applied for each color to form a colored layer.
Or the method for producing the color filter according to item 2. 4. The production of a color filter according to claim 1 or 2, wherein instead of the coating in claim 3, a desired pattern is repeated by screen printing for each color, and exposure and curing are carried out to form a colored layer. Method.