JPH0713016A - Coloring composition for color filter - Google Patents

Abstract

PURPOSE:To provide a coloring compsn. for the production of an optical color filter used for a color TV, liquid crystal color display, and camera, etc. CONSTITUTION:This coloring compsn. consists of a dispersion of coloring agent in a transparent resin. The coloring agent is obtd. by mechanically kneading a mixture of org. pigment (A), synthetic resin (B) which is solid at room temp. and insoluble with water, water-soluble inorg. salt (C) and water-soluble org. solvent (D) which at least partly dissolves (B), then removing (C) and (D) by washing with water, and drying. Thereby, the obtd. color filter has excellent heat resistance and solvent resistance and good spectral characteristics.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring composition for producing an optical color filter used in color televisions, liquid crystal color displays, cameras and the like. More specifically, it relates to a coloring composition for a color filter for forming a pattern portion generally called a stripe filter or a matrix filter.

[0002]

2. Description of the Related Art A color filter is one in which three or more fine bands (stripe) of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or fine pixels are arranged vertically and horizontally. It is made up of those placed in. The width of the stripe is a few tens of microns, and the pixels of the matrix are a few hundreds to 200 microns.
Moreover, they are arranged in order in a predetermined order for each hue. For this reason, various methods have been conventionally proposed for manufacturing color filters.

[0003] A dyeable photosensitive material is applied to a substrate such as glass, and then pattern exposure of one filter color is performed. Then, an unexposed portion is washed off in a developing process, and the remaining pattern portion is removed by the filter color. The method of sequentially repeating the operation of dyeing with the dye for all the filter colors has a high transmittance because the dye is used, and is very excellent in the quality of the color filter. However, this method has a problem in light resistance and heat resistance because it uses a dye.

Therefore, pigments having excellent light resistance and heat resistance have been used in place of dyes, but it has been difficult to obtain spectral characteristics like dyes with a color filter using pigments. That is, it was not possible to obtain a highly transparent coloring composition for a color filter simply by dispersing a pigment powder, a resin, a solvent and the like with an ordinary disperser like ordinary printing ink or paint.

In general paints, inks, etc., transparency is generally improved by decreasing the particle size of the pigment and increasing the degree of dispersion. However, in ordinary dispersers such as sand mills, three-roll mills and ball mills, primary particles are used. When it is dispersed, the transparency will not increase any more. This is because the dispersion process using an ordinary disperser mainly breaks the secondary particles into primary particles, and it is necessary to make the primary particles finer in order to further improve the transparency. The high-speed sand mill is excellent in making the pigment fine, and depending on the pigment, it is possible to make the primary particles fine, but in this case very large amounts of energy are required.

As a means for making the primary particles finer, a method is known in which a pigment dissolved in a strong acid such as concentrated sulfuric acid or polyphosphoric acid is put into cold water to precipitate the pigment as fine particles. However, the pigments that can be used are remarkably limited in terms of solubility and stability of the pigment in strong acids. Also,
It is generally very difficult to re-disperse the primary particles because the pigments finely divided by this method undergo strong secondary aggregation when dried. As another method, there is also known a method in which a pigment and a solid resin are heated and kneaded strongly with a two-roll or Banbury mixer. However, since pigments generally grow crystals at high temperatures, this method reaches the end point when the mechanical crushing force and the crystal growth are in equilibrium, and there is a limit to the miniaturization of pigments.

Further, as a method for making the primary particles of the pigment finer, a mixture of the pigment and a water-soluble inorganic salt such as salt is moistened with a small amount of solvent, and after kneading with a kneader or the like,
There is a method of removing the inorganic and solvent by washing with water and drying to obtain a pigment with fine primary particles. This method also causes strong secondary agglomeration of the pigment during drying, and in order to prevent this, generally, a method of adding rosin or a rosin derivative at the time of kneading the kneader is adopted. However, since it contains rosin or a rosin derivative, the binder resin is limited in terms of compatibility with the binder of the dispersion, and the heat resistance and solvent resistance of the rosin or rosin derivative are inferior. There was a limit to the durability of the coating film formed.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, as a crushing aid of an inorganic salt, a synthetic resin is used in combination to mechanically produce primary particles of an organic pigment. The present invention has been found out that a coloring composition obtained by dispersing a finely divided coloring agent in a transparent resin gives a coating film which is transparent and has excellent durability.

[0009]

The present invention provides a coloring composition for a color filter comprising a transparent resin and a colorant dispersed therein, wherein the colorant is an organic pigment (A), a synthetic resin which is solid at room temperature and insoluble in water. Mechanically kneading a mixture containing (B), a water-soluble inorganic salt (C) and a water-soluble organic solvent (D) that at least partially dissolves (B) (hereinafter, this step is referred to as salt milling),
A colored composition for a color filter, which is a coloring agent obtained by removing (C) and (D) by washing with water and then drying.

More specifically, the salt milling method is described in more detail by adding a small amount of a wetting agent to a mixture of an organic pigment (A), a water-insoluble synthetic resin (B) which is solid at room temperature and a water-soluble inorganic salt (C). After adding the organic solvent (D) in (1) and kneading it strongly with a kneader, put it in water and stir it with a high-speed mixer to form a slurry. Then, the slurry is filtered, washed with water and dried to obtain a pigment coated with the synthetic resin (B) (hereinafter referred to as a treated pigment). When an untreated pigment (not subjected to salt milling treatment) is used by dispersing this treated pigment together with a transparent resin for forming a color filter, a solvent and the like in a usual disperser such as a sand mill or a three roll mill. Compared with the above, a coloring composition for a color filter in which a pigment is finely dispersed can be easily obtained in a short time.

Examples of the organic pigment (A) include insoluble azo pigments such as toluidine red, toluidine maroon, hansa yellow, benzidine yellow, and pyrazolone red, soluble azo pigments such as litol red, heliobordeaux, pigment scarlet, permanent red 2B, and alizarin. ，
Derivatives from vat dyes such as indanthrone and thioindigo maroon, phthalocyanines such as phthalocyanine blue and phthalocyanine green, quinacridones such as quinacridone red and quinacridone magenta, perylenes such as perylene red and perylene scarlet, isoindolinone yellow, Isoindolinone series such as isoindolinone orange, pyranthrone red, pyranthrone series such as pyranthrone orange, thioindigo series, condensed azo series,
As thioindigo-based pigments, flavanthuron yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthron orange, dianthraquinonyl red, dioxazine violet and the like are used.

Further, not only a pigment but also a dye can be used as a part of the colorant or for color matching. Examples of such dyes include disperse dyes, water-insoluble dyes such as oil-soluble dyes, and insolubilized dyes such as direct dyes, acid dyes, and basic dyes by lake formation. However, the above-described salt milling step is meaningless for dyes that are completely soluble in the synthetic resin used, and are excluded from the present invention.

A synthetic resin (B) which is solid at room temperature and insoluble in water
In addition to pure synthetic polymers, semi-synthetic polymers such as fibrin derivatives, rubber derivatives, protein derivatives and their oligomers are also included. However, it is solid at room temperature, insoluble in water,
In addition, it must be soluble in the water-soluble solvent used as the wetting agent during salt milling. Although salt milling can be performed using a liquid polymer at room temperature, this is not preferable because the treated product causes blocking when washed and dried and requires special measures for drying or redispersion. . However, when two or more kinds of polymers are used in combination for salt milling, even if some liquid polymers are used, the mixture can be used in the present invention as long as the mixture is solid at room temperature. Among these resins, especially epoxy resin and (meth)
Acrylic resin has wide versatility, and the effect of salt milling is great. In addition, it is also excellent in terms of resistance when used as a color filter.

The above-mentioned epoxy resin means an epoxide containing one or more epoxy groups in the molecule, and an epoxy resin cross-linked with a curing agent generally has almost no solubility and therefore cannot be used in the present invention. As the epoxide, bisphenol type, novolac type, alkylphenol type, resorcin type, polyglycol type, ester type, glycidyl type such as N-glycidylamine, and cycloaliphatic epoxide are used. The above (meth) acrylic resin is a copolymer of monomers of acrylic acid, methacrylic acid and their esters, alone or in a mixture, and is a radical-polymerizable monomer such as 60 mol% or less of styrene, vinyl acetate and maleic anhydride. Copolymers with and are also included. However, a three-dimensionally crosslinked polymer such as a copolymer with a polyfunctional monomer has poor solubility, and is not suitable for the present invention.

The organic solvent (D) is not particularly limited as long as it is at least partially soluble in (B) and is water-soluble, but since the temperature rises during salt milling and the solvent easily evaporates,
From the viewpoint of safety, a high boiling point solvent is preferable. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene Glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-
Ethoxy-2-propanol, dipropylene glycol,
Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, etc. are used.

In addition to the above compounds, an additive such as a dispersant or a plasticizer during salt milling and an inorganic pigment such as barium sulfate or silica which is generally used as an extender pigment may be used in combination. You may mix and process a pigment. The coloring composition for a color filter of the present invention is prepared by dispersing the colorant subjected to the salt milling treatment together with the transparent resin and the solvent, or by dispersing the colorant with the transparent resin in advance and then adding the solvent or the resin solution to disperse the colorant. And manufacture. The salt milled colorant and the transparent resin are mixed in a solid content ratio of 1/10 to 4/1.

Various dispersing means such as a three roll mill, a two roll mill, a sand mill and a kneader can be used to disperse the colorant in the transparent resin. Further, in order to improve the dispersion of these, various auxiliary agents such as various surfactants and pigment derivatives can be added as appropriate. Since the dispersion aid is excellent in dispersing the pigment and has a great effect of preventing reaggregation of the pigment after the dispersion, a color filter having excellent transparency can be obtained. In addition, when considering storage stability, a small amount of a polymerization inhibitor may be added.

The transparent resin is 400 nm to 700 nm in the visible light range.
Is a resin having a light transmittance of 80% or more, preferably 95% or more. Thermosetting resin, thermoplastic resin, oil-soluble photosensitive resin,
A water-soluble photosensitive resin, a monomer and / or an oligomer and a photoinitiator are used. However, since a high temperature heating process is performed in a later step of manufacturing the color filter, it is necessary to use a resin having good resistance also in the heating process. Further, since treatment with various solvents is also performed in the subsequent steps, solvent resistance of the formed image is also required.

Examples of the thermosetting resin and thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resin, phenol resin, polyester resin, polyamide, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin,
Cyclized rubber, rosin derivative, epoxy resin, celluloses, polybutadiene, polyimide resin, melamine resin,
Examples include urea resins.

Examples of the oil-soluble photosensitive resin include a photocrosslinking photosensitive resin of cinnamic acid, a bisazide photodegradable crosslinking photosensitive resin, and an O-quinonediazide photodegradable photosensitive resin. Examples of the water-soluble photosensitive resin include polyvinyl alcohol / stilbazolium resin. If necessary, a photocrosslinking agent such as a diazo compound, a chromium salt, a dichromate, or a bisazide compound can be used in combination with the transparent resin.

The monomers and oligomers include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, vinyl acetate, N-hydroxymethyl acrylamide, polyethylene glycol diacrylate, pentaerythritol triacrylate, styrene, vinyl acetate, various acrylic acid esters, various methacrylic acid esters , Acrylonitrile, dipentaerythritol hexaacrylate, hexaacrylate of a caprolactone adduct of dipentaerythritol hexaacrylate, melamine acrylate, epoxy acrylate prepolymer and the like. Further, a photosensitive copolymer compound obtained by introducing a photosensitive vinyl group through an isocyanate group into a vinyl copolymer compound composed of styrene, a vinyl compound having a carboxyl group and a vinyl compound having a hydroxyl group can also be used. This copolymer compound has heat resistance, solvent resistance,
Since it has excellent dispersibility and can be easily thinned, it has a good pattern shape and is suitable for forming high-quality color filters.

As the photoinitiator, benzophenone, orthobenzoyl, methyl benzoate, 2,4-diethylthioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, tetra ( t-Butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-
2-Methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, anthraquinone, 9-phenylacridine, azobisisobutyronitrile, benzoin alkyl ether, thioacridone, N- [alkylsulfonyloxy]- Examples include 1,8-naphthalenedicarboximide, 2,3,6-tri [trichloromethyl] triazine, benzanthrone / triethanolamine, methylene blue / benzenesulfinate, carbon tetrachloride / manganese carbonyl, and the like.

The coloring composition for a color filter has a colorant composition of 0.2 to 0.2 in order to sufficiently disperse the colorant.
Use solvent to coat to a thickness of 5 microns. Examples of the solvent include cyclohexanone, cellosolve acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, Examples include isobutyl ketone and petroleum-based solvents, which may be used alone or in combination.

Using the coloring composition for a color filter of the present invention, a printing ink for a gravure offset printing machine, a printing ink for a waterless offset printing machine, a screen ink for a silk screen printing machine, an alkali developing resist agent, etc. are produced. be able to. These printing inks, alkaline development type resist agents, etc. are manufactured by removing coarse particles of 5μ or more, preferably 1μ or more and mixed dust by means of centrifugal separation, sintering filter, membrane filter, etc. To do.

Since the above printing ink can be patterned by simply repeating printing and drying, it is a low cost and excellent in mass productivity as a method of manufacturing a color filter. further,
With the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. Also, if there is swelling or dissolution of the blanket,
As a result, the reproducibility of the pattern and the transparency are deteriorated, and various cautions are required in selecting the solvent for the printing ink. Further, it is important to control the fluidity of the ink on the printing machine, and the ink viscosity can be adjusted by the extender pigment.

The above alkali developing resist agent is applied onto a glass substrate by a coating method such as spray coating or spinner coating. The dried film is 0.2 to 5 microns and is exposed to UV light through a positive or negative mask with a predetermined pattern, with or without contact. After that, the uncured portion is removed by dipping or spraying with an alkaline developer and the same operation is repeated. Furthermore, in order to accelerate the polymerization of the photosensitive resin, heating can be performed if necessary.

At the time of development, an aqueous solution of sodium carbonate, caustic soda or the like is used as an alkali developing solution, and amines such as dimethylbenzylamine and triethanolamine can be added. In order to increase the ultraviolet exposure sensitivity, a film that prevents oxygen inhibition was formed by applying and drying an alkali-developable resist agent and then applying and drying a water-soluble or alkali-water-soluble resin, such as a water-soluble acrylic resin or polyvinyl alcohol resin. After that, ultraviolet exposure can be performed.

[0028]

EXAMPLES The present invention will be described below based on examples.
In the examples, “part” means “part by weight” and “%” means “% by weight”. Prior to the examples, production examples of salt milled pigments and resin synthesis examples will be shown. (Production Example 1 of salt-milled pigment) Phthalocyanine-based pigment (“Rionol Blue E manufactured by Toyo Ink Mfg. Co., Ltd.
S ”) 250 g, sodium chloride 700 g, epoxy resin (Yukaka Shell Co., Ltd.“ Epicoat 1004 ”) 90 g and polyethylene glycol (Tokyo Kasei“ Polyethylene glycol 3
00 ") 160 g was charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 3 hours. Next, this mixture was poured into 2.5 liters of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 80 ° C to form a slurry, which was then filtered and washed with water to remove sodium chloride and solvent. The epoxy-treated pigment was obtained by drying in a hot air oven at ℃ for about 24 hours.

(Production Example 2 of salt-milled pigment) 280 g of a phthalocyanine pigment ("Rionol Green 2YS" manufactured by Toyo Ink Mfg. Co., Ltd.) was used in place of "Rionol Blue ES" in Production Example 1 An epoxy treated pigment having good transparency and various resistances was obtained by the same treatment as described above. (Production Example 3 of salt milled pigment) Instead of "Rionol Blue ES" in Production Example 1, a benzimidazolone-based pigment ("Rionogen Yellow 3 manufactured by Toyo Ink Mfg. Co., Ltd."
G ") was treated in the same manner as in Production Example 1 to obtain an epoxy-treated pigment having excellent transparency and various resistances.

(Production Example 4 of salt milled pigment) Instead of 90 g of "Epicoat 1004" and 160 g of "polyethylene glycol 300" in Production Example 1, an acrylic oligomer ("John Cryl 682" manufactured by Johnson Wax Co., Ltd.) 10
Using 0 g and diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) 160 g, the same treatment as in Production Example 1 was carried out to obtain an acrylic treated pigment. (Production Example 5 of salt milled pigment) 240 g of perylene-based pigment ("Rionogen Red GD" manufactured by Toyo Ink Mfg. Co., Ltd.) was used instead of "Rionol Blue ES" in Production Example 1 in the same manner as in Production Example 1. After treatment, an epoxy-treated pigment having good transparency and various resistance was obtained.

Production Example 6 of Salt Milled Pigment Production Example 1 In place of “Rionol Blue ES”, 255 g of dioxazine pigment (“Rionogen Violet RL” manufactured by Toyo Ink Mfg. Co., Ltd.) was used. By the same treatment, an epoxy-treated pigment having good transparency and various resistances was obtained. (Production Example 7 of salt-milled pigment) Instead of 250 g of "Lionol Blue ES" of Production Example 4, 255 g of "Rionogen Violet RL" was used and treated in the same manner as in Production Example 4 to obtain transparency and various resistances. A good acrylic treated pigment is obtained.

(Synthesis of IPDI Adduct) After heating 222 parts of isophorone diisocyanate (IPDI) to 80 ° C. in a 1 L four-neck flask in a nitrogen stream, 116 parts of 2-hydroxyethyl acrylate and 0.13 parts of hydroquinone were added over 2 hours. The mixture was added dropwise and then reacted at 80 ° C for 3 hours to obtain a compound having one liquid isocyanate group and one vinyl group (IPDI
I got an adduct).

(Synthesis Example a) A 1 L four-necked flask was charged with 175.0 parts of diethylene glycol dimethyl ether.
Styrene 8.8 parts, 2-hydroxymethacrylate 43.8 parts,
Charge 26.3 parts of methacrylic acid and 96.3 parts of ethyl methacrylate and heat to 90 ° C. Diethyl glycol dimethyl ether 145.0 parts, styrene 8.8 parts, 2-hydroxymethacrylate 43.8 parts, methacrylic acid 26.3 parts, ethyl methacrylate 96.3 parts and benzoyl peroxide. (Niiper BMT manufactured by Nippon Oil & Fats Co., Ltd.) A mixture of 2.92 parts dissolved therein was added dropwise over 3 hours and reacted at 90 ° C for 3 hours. In addition, “Nyper B
MT "1.75 parts to diethylene glycol dimethyl ether 10
What was dissolved in part was added and the reaction was continued for 1 hour. Next, the temperature inside the flask was set to 80 ° C., 34.3 parts of IPDI adduct and 0.02 part of tin octylate dissolved in 20 parts of diethylene glycol dimethyl ether were added dropwise over about 10 minutes, and the reaction was carried out for 2 hours after the addition. The acid value of the reaction product was about 90.

(Resin Synthesis Example b) In a 1 L four-necked flask, 175.0 parts of diethylene glycol dimethyl ether,
Styrene 17.5 parts, 2-hydroxymethacrylate 43.8 parts,
Charged with 26.3 parts acrylic acid and 87.7 parts butyl methacrylate
It was heated to 90 ℃ and mixed and dissolved in advance with 140.0 parts of diethylene glycol dimethyl ether, 17.5 parts of styrene, 43.8 parts of 2-hydroxymethacrylate, 26.3 parts of acrylic acid, 87.7 parts of butyl methacrylate and 2.92 parts of "Nyper BMT" in 3 hours. It was dropped and reacted at 90 ° C. for 3 hours. Further, 1.75 parts of "Nyper BMT" dissolved in 10 parts of diethylene glycol dimethyl ether was added, and the reaction was continued for 1 hour. Next, the temperature inside the flask was adjusted to 80 ° C., 45.5 parts of IPDI adduct and 0.13 part of tin octylate dissolved in 25 parts of diethylene glycol dimethyl ether were added dropwise over about 10 minutes, and the reaction was carried out for 2 hours after the addition. The acid value of the reaction product is about
It was 105.

(Resin Synthesis Example c) A 1 L four-necked flask was charged with 175.0 parts of cyclohexanone, 43.8 parts of styrene, 43.8 parts of 2-hydroxyacrylate, 35.0 parts of acrylic acid and 52.5 parts of butyl methacrylate and heated to 90 ° C. 145.0 parts of cyclohexanone, 43.8 parts of styrene, 43.8 parts of 2-hydroxy acrylate, 35.0 parts of acrylic acid, 52.5 parts of butyl methacrylate and 1.75 parts of azobisisobutyronitrile were mixed and dissolved and added dropwise over 3 hours at 90 ° C. Was reacted for 3 hours. Further, 0.70 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and 1
The reaction continued for an hour. Next, the temperature inside the flask was set to 80 ° C and IP
A solution prepared by dissolving 38.2 parts of DI adduct and 0.13 part of tin octylate in 20 parts of cyclohexanone was added dropwise in about 10 minutes and reacted for 2 hours after the addition. The acid value of the reaction product was about 140.

(Resin Synthesis Example d) A 1 L four-necked flask was charged with 175.0 parts of cyclohexanone, 26.3 parts of styrene, 43.8 parts of 2-hydroxyacrylate, 35.0 parts of acrylic acid and 70.0 parts of butyl methacrylate and heated to 90 ° C. Cyclohexanone 145.0 parts, styrene 26.3 parts, 2-hydroxy acrylate 43.8 parts, acrylic acid 35.0 parts, butyl methacrylate 70.0 parts and azobisisobutyronitrile 1.75 parts were mixed and dissolved, and the mixture was added dropwise over 3 hours at 90 ° C. Was reacted for 3 hours. Further, 0.70 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and 1
The reaction continued for an hour. Next, the temperature inside the flask was set to 80 ° C,
About 23.5 parts of isocyanate ethyl methacrylate and 0.11 part of tin octylate dissolved in 20 parts of cyclohexanone
The mixture was added dropwise over 10 minutes and reacted for 2 hours after the addition. The acid value of the reaction product was about 145.

Example 1 (1) Preparation of Red Resist Resin Synthesis Example a 12.51 Parts Salt Milled Pigment 5 7.30 parts Salt Milled Pigment 3 2.45 parts Dispersant 0.43 parts Diethylene glycol dimethyl ether 42 0.87 parts were mixed and dispersed in a sand mill for 20 minutes to prepare a red paste. Next, red paste 65.56 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.56 parts Irgacure 907 (manufactured by Ciba Geigy) 0.12 parts Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.12 parts Kayacure EPA (manufactured by Nippon Kayaku) Yakusha) 0.06 parts Diethylene glycol dimethyl ether 31.83 parts were mixed thoroughly in a stirrable container and filtered through a 1.0 μ filter to prepare a red resist having a nonvolatile content of about 20%.

(2) Preparation of green resist Resin synthesis example a 13.62 parts Salt milled pigment 2 6.97 parts Salt milled pigment 3 1.67 parts Dispersant 0.39 parts Diethylene glycol dimethyl ether 47.87 parts , And dispersed in a sand mill for 20 minutes to produce a green paste. Then green paste 71.68 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 3.90 parts Irgacure 907 (manufactured by Ciba Geigy) 0.18 parts Kayacure DETX (manufactured by Nippon Kayaku Co.) 0.18 parts Kayacure EPA (manufactured by Nippon Kayaku) (Yakuhin Co., Ltd.) 0.09 parts Diethylene glycol dimethyl ether 47.69 parts were thoroughly mixed in a stirrable container and filtered with a 1.0 μ filter to prepare a green resist having a nonvolatile content of about 20%.

(3) Preparation of blue resist Resin synthesis example a 13.54 parts Salt milled pigment 1 5.82 parts Salt milled pigment 6 1.67 parts Dispersant 0.39 parts Diethylene glycol dimethyl ether 37.87 parts Then, it was dispersed in a sand mill for 20 minutes to produce a blue paste. Blue paste 59.84 parts NK ester ATMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) 4.30 parts Irgacure 907 (manufactured by Ciba Geigy) 0.22 parts Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) 0.22 parts Kayacure EPA (manufactured by Nippon Kayaku) 0.11 part Diethylene glycol dimethyl ether 34.32 parts were thoroughly mixed in a stirrable container and filtered with a 1.0 μ filter to prepare a blue resist having a nonvolatile content of 20%.

The obtained red resist is microfiltered with a 1 μm filter, and spin-coated on a glass substrate on which a black matrix is already patterned to a film thickness of 1.3 μm after solvent drying with a spin coater. did.
Next, after prebaking at 60 ° C. for 20 minutes, a polyvinyl alcohol aqueous solution was spin-coated, the water was dried, and then exposure was performed using a photomask for pattern formation. It was developed with a 1% aqueous solution of sodium carbonate, washed with pure water, and then post-baked at 230 ° C. for 1 hour. Hereinafter, green and blue patterns were formed by the same method to fabricate a color filter.

Example 2 A color filter was prepared in the same manner as in Example 1 except that the blue resist described in Example 1 was replaced with the following blue resist. Resin Synthesis Example a 13.74 parts Salt milled pigment 4 5.87 parts Salt milled pigment 7 1.70 parts Dispersant 0.37 parts Diethylene glycol dimethyl ether 37.57 parts are mixed and dispersed in a sand mill for 20 minutes. , Blue paste was prepared. Then, in the same manner as in Example 1, a blue resist having a nonvolatile content of about 20% was prepared.

[Examples 3 to 5] Color filters were produced in the same manner as in Example 1 except that the resins, monomers and initiators shown in Table 1 were replaced. However, the values in parentheses in the table are weight ratios, DPHA is Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.), and B-CIM is B-CIM (Hodogaya Chemical Co., Ltd.).

Comparative Example 1 (1) Preparation of Red Resist Resin Synthesis Example a 12.55 Parts Untreated “Rionogen Red GD” 7.20 parts Untreated “Rionogen Yellow 3G” 2.40 parts Dispersant 0 0.51 part Diethylene glycol dimethyl ether 42.89 parts were mixed and dispersed in a sand mill for 20 minutes. However, sufficient dispersion was not obtained and transparency was insufficient. Therefore, 40 more
It was dispersed for a minute to make a red paste. Then, a red resist was prepared in the same manner as in Example 1. Compared to Example 1, the filtration amount of the resist is small, so that the filtration time is long,
The workability of manufacturing was poor.

(2) Preparation of green resist Resin synthesis example a 12.51 parts Untreated "Rionol Green 2YS" manufactured by the manufacturer) 8.91 parts Untreated "Rionogen Yellow 3G" 1.65 parts Dispersant 0. 55 parts Diethylene glycol dimethyl ether 46.95 parts were mixed and dispersed in a sand mill for 20 minutes, but sufficient dispersion was not obtained and transparency was insufficient. Therefore, 40 more
It was dispersed for a minute to make a green paste. Then, a green resist was prepared in the same manner as in Example 1. Compared to Example 1, the filtration amount of the resist is small, so that the filtration time is long,
The workability of manufacturing was poor.

(3) Preparation of Blue Resist Resin Synthesis Example a 13.54 Parts Untreated “Lionol Blue ES” 5.66 parts Untreated “Rionogen Violet RL” 1.42 parts Dispersant 0.39 parts Diethylene glycol dimethyl ether Although 37.87 parts were mixed and dispersed for 20 minutes by a sand mill, sufficient dispersion was not obtained and transparency was insufficient. So, 20 more
It was dispersed for a minute to make a blue paste. Then, a blue resist was prepared in the same manner as in Example 1. Compared to Example 1, the filtration amount of the resist is small, so that the filtration time is long,
The workability of manufacturing was poor. Using the obtained red, green and blue resists, a color filter was produced in the same manner as in Example 1.

The performance of each color resist obtained in Examples 1 to 5 and Comparative Example 1 was evaluated by the following method. The results are shown in Table 2. 1. Coatability The state of the coating film (presence or absence of pinholes and repellency) when coated with a spin coater to a film thickness of 1.5 μm is visually evaluated. 2. Developability, sensitivity and resolution A test chart (Toppan Printing Co., Ltd. line width 0.5 to 50.0 μm was applied on the coating film obtained by coating and drying with a spin coater.
The optimum value of the exposure amount and development time when developing with a 1% aqueous solution of sodium carbonate and the resolution at that time are evaluated by irradiating with ultraviolet light at 10-40 mJ / cm ² through m). 3. The coating film obtained in the same manner as the transmittance 2 was heated for 60 minutes in a hot air circulation drying oven at 230 ° C, and the transmittance of the cured coating film obtained (red resist 610 nm, green resist 540 nm, blue resist 46
0 nm) was measured by a spectrophotometer (manufactured by Hitachi Ltd.).

4. Surface hardness Measure the surface hardness of the cured coating film obtained in the same manner as 3 by the test method specified in JIS K 5400. 5. Hot air convection drying oven for cured coatings obtained in the same way
Change in transmittance at a specified wavelength (same as 3) before and after heating at 250 ° C for 60 minutes. 6. The film thickness before and after heating of the cured coating film obtained in the same manner as in 3
The film reduction rate measured by a surface profiler (Dektak3030 manufactured by Nippon Vacuum Technology Co., Ltd.) and calculated by the following formula. 7. Chemical resistance For IPA resistance, after setting the cured coating film obtained in the same way as in 3 in IPA vapor for 5 minutes, for other resistance, soak it in various organic solvents or 5% sodium hydroxide aqueous solution for 30 minutes. After that, visually observe the presence or absence of the interface of the immersion part.

[0048]

[Table 1]

[0049]

[Table 2]

Example 6 A separable flask was charged with 600 parts of diethylene glycol monobutyl ether and 400 parts of ethylene glycol monobutyl ether, and an epoxy resin (“Epicoat 1007” manufactured by Shell Chemical Co., Ltd.) was introduced at about 100 ° C. while introducing nitrogen gas. ) 600 parts was gradually added and dissolved, and the temperature was raised to 130 ° C to produce a varnish. A treated pigment, a dispersant, and a solvent were added to this varnish and dispersed by a three-roll mill to produce red, green, and blue inks.

Red ink varnish 31.82 parts Salt milled pigment 5 7.30 parts Salt milled pigment 3 2.45 parts Precipitating barium sulfate 0.72 parts Dispersant 0.52 parts Diethylene glycol monobutyl ether 0.64 parts Ethylene Glycol monobutyl ether 0.20 parts

Green ink varnish 50.35 parts Salt milled pigment 2 6.97 parts Salt milled pigment 3 1.67 parts Precipitating barium sulfate 0.86 parts Dispersant 0.49 parts

Blue ink varnish 53.92 parts Salt milled pigment 1 5.82 parts Salt milled pigment 6 1.66 parts Precipitating barium sulfate 0.36 parts Dispersant 0.52 parts Diethylene glycol monobutyl ether 0.10 parts

The obtained red ink was filtered through a 1 μ filter, then applied on an intaglio plate having a dot matrix of 150 μ × 150 μ, and the excess ink was scraped off with a doctor. After transferring the ink on the intaglio plate to the blanket, bring the blanket into contact with the glass substrate for the color filter,
The ink on the blanket was transferred to a glass substrate. Repeat the same operation below to set the green and blue patterns to 100.
It was formed over a size of mm × 100 mm. The obtained pattern was heat-treated at 200 ° C. for 1 hour to produce a color filter. This color filter has a film thickness of 2μ and a transmittance of red 91
%, Green 79%, blue 82%. In addition, the change in spectral transmittance when stored at 220 ° C for 1 hour is within 5%, and the change in spectral transmittance when irradiated with a xenon lamp for 120 hours through a deflection filter is within 5%. The state of the printed surface after immersion in a 5% hydrochloric acid solution, a 5% sodium hydroxide solution, toluene, acetone, N-methyl-2-pyrrolidone, and isopropyl alcohol at 25 ° C for 10 minutes was good.

Comparative Example 2 In the same manner as in Example 6, red, green and blue inks having the following formulations were produced. Red ink varnish 31.92 parts Untreated "Rionogen Red GD" 7.20 parts Untreated "Rionogen Yellow 3G" 2.40 parts Precipitating barium sulfate 0.72 parts Dispersant 0.52 parts Diethylene glycol monobutyl ether 0. 64 parts Ethylene glycol monobutyl ether 0.20 parts

Green ink varnish 50.56 parts Untreated "Lionol Green 2YS" 8.91 parts Untreated "Rionogen Yellow 3G" 1.65 parts Precipitating barium sulfate 0.86 parts Dispersant 0.49 parts

Blue Ink Varnish 54.02 parts Untreated “Lionol Blue ES” 5.66 parts Untreated “Rionogen Violet RL” 1.42 parts Precipitating barium sulfate 0.36 parts Dispersant 0.52 parts Diethylene glycol mono Butyl ether 0.10 parts

Using the obtained red, green and blue inks, a color filter was prepared in the same manner as in Example 6. This color filter has a film thickness of 2μ, transmittance of 84% red, 73% green, and blue.
It was 77%. Also, the change in spectral transmittance when stored at 220 ° C for 1 hour is within 5%, and the change in spectral transmittance when irradiated with a xenon lamp for 120 hours through a deflection filter is 5%.
Within the range, resistance to various solvents (similar to Example 6)
Was good.

[0059]

According to the present invention, it is possible to obtain a high-quality color filter which is excellent in heat resistance, solvent resistance and dispersibility, can be easily formed into a thin film, and has a good pattern shape. Further, it is possible to manufacture a color filter having excellent spectral characteristics that can cope with thinning and size increase.

Front page continuation (72) Inventor Yasuharu Iida 2-33-1 Kyobashi, Chuo-ku, Tokyo Toyo Inki Manufacturing Co., Ltd. Incorporated (72) Inventor Hitani Tani 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd.

Claims (1)

[Claims] 1. A coloring composition for a color filter, comprising a transparent resin and a colorant dispersed therein, wherein the colorant is an organic pigment.
A mixture containing (A), a water-insoluble synthetic resin (B) that is solid at room temperature, a water-soluble inorganic salt (C) and a water-soluble organic solvent (D) that at least partially dissolves (B) is mechanically treated. Kneading, (C) and (D)
A coloring composition for a color filter, which is a colorant obtained by washing and removing water, and then drying.