JPH01168775A - Color filter ink, colored indicator panel, and liquid crystal display panel - Google Patents

Abstract

PURPOSE:To obtain the title ink which has excellent applicability and color forming properties and gives a color filter capable of showing a vivid color under transmitted light, by mixing a specified coloring agent, a resin component, a solvent, and various additives. CONSTITUTION:An anionic dye (a) having organic groups, such as an acid dye, acid mordant dye or direct dye having an acid group such as -SO3H or -COOH in the molecule, is reacted with an organic compound (b) having cationic groups by stirring in a solvent at 50-100 deg.C for 1-7hr to give a coloring agent. This coloring agent is mixed with a resin component (e. g., a polyester resin), a solvent (e. g., a higher alcohol) and, if required, various additives, such as an (extender) pigment, a drying inhibitor, and a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention particularly relates to colored display panels such as liquid crystal panels of liquid crystal color televisions and inks therefor.

Conventional technologyLCD color televisions are widely used;
A color filter with a pattern consisting of a red, blue, and green dot matrix is installed on a transparent plate such as a glass plate.
A liquid crystal panel is used in which an electrode is provided corresponding to each dot of the color filter, and a liquid crystal layer is sandwiched between transparent plates on top of the electrode.

Manufacturing methods for color filters for liquid crystal panels can be broadly classified into two types. One method is to dye a resist film, such as gelatin, patterned in advance for each color with an acid dye. In this method, a photosensitive film is exposed and baked using a photographic method, developed to remove the unexposed areas to form a resist film, and this is dyed with an acid dye.
It is excellent in terms of high dimensional accuracy and vivid colors.

Another method is to print a color pattern with ink containing dispersed pigments. This method only requires pattern printing with red, blue, and green ink, and unlike the above-mentioned photographic method, it does not require development, making it easy to manufacture and suitable for mass production, reducing manufacturing costs. Excellent in what it can do.

Problems to be Solved by the Invention However, the method using the first photographic method is limited to red, blue,
Since it is necessary to create a patterned resist film for each color of green in advance, each process of applying photosensitive liquid, baking, developing, and dyeing must be repeated three times, making the process complicated and manufacturing costs high. There is.

The problem with the method of using ink that uses pigment as the second coloring agent is that the resulting color filter has poor translucency due to the pigment, and the translucency of blue in particular is poor, making it impossible to produce clear colors. There is.

Means for Solving the Problems In order to solve the above problems, the present invention is characterized in that it contains a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group as a coloring agent. The purpose of the present invention is to provide ink for color filters.

Another object of the present invention is to provide a colored display board characterized by having a colored coating film containing a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group as a coloring agent.

Further, it provides a liquid crystal display panel characterized in that a colored coating film containing a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group as a coloring agent is used as a color filter for a liquid crystal display. It's about doing.

Next, the present invention will be explained in detail.

In the present invention, a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group is used as a coloring agent. Examples include acid dyes, acid mordant dyes, direct dyes, etc., but specifically, when expressed by color index, the following acid dyes are preferable.

Yellow CI Ac1d Yellow 17, 49, 6
7, 72, 127, 110, 135, 161
, Red CT Ac1d Red 37, 50, 1111 114, 257, 266, 317, Blue CI Ac1d Blue 41, 83, 90,
113, 125, 129, 182, CI Ac1d Orange 7, 56, CI Ac1d Green 25, 41, CI Ac1d Violet 97, 27, 2
48 etc. can be cited.

These anionic dyes can be used in the form of salts such as sodium salts, and not only those with high purity but also those containing inorganic salts such as boron sulfate and common salt can be used. These metals and salts can be easily dissolved and removed by purification means such as washing with water after obtaining a reaction product of an anionic dye or its salt and an organic compound having a caraonic group.

The organic compound having a cationic group used in the present invention is represented by (';N'-)χ-, and the nitrogen substituent is hydrogen, an alkyl group, a cyclic group (
Examples include those having a substituent (including those having a substituent), and examples of such agents include, but are not limited to, those known as cationic activators.

As a cationic activator, alkylbenzyldimethyl,
Ammonium salts of dimethyldialkyl or alkyltrimethyl, or alkylpyridium salts can be used. Among the commercially available cation activators, quaternary ammonium salts such as tetradecyldimethylbenzylammonium chloride and octadecyltrimethylammonium chloride are preferred, but others include coconut dimethylbenzylammonium chloride, coconut alkylamine hydrochloride, and tetradecylamine. Hydrochloride, octadecylamine hydrochloride, N-tallow alkyl N, N.

N'N+-pentamethylpropylene diammonium dichloride, tallow alkylpropylene diamine acetate, 1
-Hydroxy ethyl 2-alkyl (hardened beef tallow) imidacillin quaternary salt, coconut alkylisoquinolinium bromide, dihardened beef tallow alkyldimethylammonium chloride, dioleyldimethylammonium chloride, and the like.

To obtain a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group, the anionic dye having an organic acid group is dispersed or dissolved in, for example, alcohol, aromatic hydrocarbon, etc. Stir at 100°C for 1 to 7 hours. These reaction products can also be obtained by kneading means such as mixing an anionic dye having an organic acid group and an organic compound having a cationic group together with a solvent in a ball mill for 20 to 30 hours. At this time, resins may be mixed, and the method described in detail in Japanese Patent Publication No. 3B-26088 can be used.

In order to prepare the color filter ink of the present invention, for example, a mixed resin of a drying oil and a rosin-modified phenolic resin and/or a petroleum resin, a drying oil-modified alkyd resin, a polyester resin, an epoxy resin, an acrylic molemer or an oligomer is used. A resin component such as ultraviolet ray or electron beam curable resin, a coloring agent obtained from the above-mentioned anionic dye and an organic compound having a cationic group, a solvent, and various auxiliary agents are added, and these are mixed into a three-roll etc. Mixed or kneaded using kneading means. The above resin components include:
In particular, ultraviolet or electron beam curable resins containing polyester-amino resins, acrylic molemer or oligomers are preferred.When used as coating film components of color filters of liquid crystal panels, these resins can be used to form electrodes by sputtering. Even if it is exposed to a high temperature of 190° C. for 1 hour for a long time, its deterioration can be reduced and yellowing can be avoided, making it suitable as a coating film for liquid crystal displays that require clear colors.

As an auxiliary agent used in the ink of the present invention, general pigments such as cyanine green and extender pigments with good transparency can also be used in combination, if necessary. Examples of extender pigments include silica, talc, and precipitated barium sulfate. These are mainly used for adjusting the viscosity of ink. In addition, when using a drying oil type ink, a dryer to promote polymerization and a drying inhibitor during ink storage are used, and in the case of ultraviolet curable ink, a photopolymerization initiator and the like are used as necessary. Furthermore, in order to improve the printability of the ink, aliphatic hydrocarbons, aromatic hydrocarbons, higher alcohols, high-boiling point ethylene glycol or monoalkyl ether of diethylene glycol, etc. are used as the solvent.

The ink of the present invention is preferably used as a lithographic offset ink. When using an oil-soluble vehicle, things such as acidic dyes are difficult to disperse, but products modified with organic compounds having cationic groups as described above can be easily dispersed or dissolved in the oil-soluble vehicle. For this purpose, the organic compound having a cationic group is preferably one having a relatively long-chain hydrocarbon substituent.

The ink of the present invention is not limited to lithographic offset ink.
By adjusting the ink vehicle appropriately, it can also be used in letterpress offset inks, intaglio offset inks, screen printing inks, etc., and is used in each type.

The colored display plate of the present invention is produced by applying the ink of the present invention to a transparent plate using the above-described printing method, etc., but it is used for large displays used outdoors and other devices that require clear colors in transmitted light. Used for display boards.

In addition, the liquid crystal panel of the present invention is used, for example, in a liquid crystal color television, and is manufactured by a conventional manufacturing method.For example, as described above, the ink of the present invention is applied to glass and dried (usually including curing). A color filter coating film is formed, a protective film such as an epoxy resin is provided on the coating film, and a transparent electrode film is formed thereon by sputtering or the like. This transparent electrode film is etched to correspond to the red, blue, and green dots or stripes of the color filter, and the liquid crystal is further sandwiched between glass plates. The liquid crystal panel created in this way is illuminated with a bank light and when electrical signals based on image signals are applied to the electrodes corresponding to each color,
The liquid crystal is classified as transparent or opaque depending on whether it is on or off, so when it is transparent, the dots of the corresponding color on the color filter shine, allowing images to be displayed.

Example Next, the present invention will be explained in detail.

[Preparation of colorant]

CI Ac1d as a dye consisting of a compound of the following structural formula
Put 10 g of Blue 90 (Blue 5P, manufactured by Nippon Kayaku @) sushi 2-member 5 into a 100 cc Erlenmeyer flask, add 10 cc of isopropyl alcohol and 10 cc of toluene, stir at room temperature for 30 minutes to dissolve, and add tetradecyldimethylbenzyl to this. After adding 12 g of Tsusan cation M2-100 (manufactured by NOF ■) to ammonium chloride, 8
The reaction was carried out by heating and stirring at 0° C. for 5 hours.

After that, it was cooled to room temperature, and the resulting dye lake was mixed with distilled water.
After adding 0 cc and washing, water was removed by decantation to obtain 17 g of paste of oil-dispersible dye lake (A). When I looked at this dye lake (A) with an electron microscope, I found that
The particle size of the particles was 0.5 μm or less.

[Preparation of polyester resin for vehicle] II! Heat 128 parts by weight of trimellitic anhydride, 18.5 parts by weight of phthalic anhydride, 18.5 parts by weight of adipic acid, 312 parts by weight of neopentyl glycol, and 10% of pheasant in a four-bottle flask for 150 minutes to obtain an acid value of 14 to 10. 17 resins were obtained.

After this, it was left to cool to 150℃, and then trimellitic anhydride 6
After adding 4 parts by weight and stirring for 90 minutes, Diadol 1
Add 55 parts by weight of 35 (higher alcohol manufactured by Mitsubishi Kasei ■), cool to 70°C, add 200 parts by weight of hexamethoxymethylolmelamine and 110 parts by weight of Diadol 135 to obtain a polyester resin (A) with an acid value of 40 to 45. was prepared.

[Preparation of ink]

The following formulation was kneaded using three rolls to produce blue ink.

Dye Lake (A) obtained above 10 parts by weight Polyester resin (A) obtained above 75 parts by weight Silica (Aerosil I 200, 5 parts by weight manufactured by Nippon Aerosil Co., Ltd.) Diadol 135 (manufactured by Mitsubishi Kasei@) 10 parts by weight (
High alcohol having 13 to 15 carbon atoms) 100 parts by weight [Preparation of color filter] Attach a waterless lithographic plate made by Eastside to an offset proofing printer, print the above blue ink on a glass plate, and print at 180°C for 10 minutes. A blue color filter was obtained by printing.

[Evaluation of color filter]

As a result of photographing the spectrum of the color filter obtained above, there was a peak wavelength at 456 na+, and its transmittance was 85%.

You can also use this color filter with isopropyl alcohol,
The dye lake used as a coloring agent (
There was no elution or fading of A).

Comparative Example In Example 1, instead of using dye lake (A), cyanine blue and Fastogen Super Violet) were used.
An ink was prepared in the same manner as in Example 1, except that a mixed pigment containing RNS (manufactured by Dainippon Ink & Chemicals) was used in a 4:1 mixture, and a color filter was prepared by printing this on glass in the same manner as in Example 1.

When the spectrum was taken in the same manner as in Example 1, the peak wavelength was 460r+m and the transmittance was 7.
It was 0%. Note that, as in Example 1, there was no elution or fading of the pigment.

Example 2 [Preparation of colorant] CI Ac1d Blue 90 (Polar Cyanine G1
(manufactured by Ciba Geigy) (contains inorganic salt) 10g in Example 1
In the same manner as above, tetradecyldimethylbenzyl ammonium chloride was reacted with 11 g of Ssancation M2-100 (manufactured by NOF Corporation) and washed with distilled water to obtain 14.5 g of paste of dye lake (B). This dye lake (
When we looked at the particles in B) using an electron microscope, we found that their particle size was 0.
It was 5 μm or less.

[Preparation of ink]

The following formulation was kneaded using three rolls to produce an ultraviolet curable blue ink.

Dye lake (B) obtained above 10 parts by weight Epoxy acrylate 45 parts by weight (Lipoxy 5P-1509, Showa Kobunshi side layer) Dipentaerythritol hexa 35 parts by weight Acrylate precipitated barium sulfate (Purifine BP-1, 5 parts by weight (Manufactured by Sakai Chemical) 2.2~Dimethoxy-2-phenyl 5 parts by weight Acetophenone (Irgacure 651, manufactured by Ciba Geigy) t-Butylhydroquinone 0.1 part by weight 100
, 1 part by weight [Preparation of color filter] The above ink was printed on a glass plate using an offset proofing printer in the same manner as in Example 1, and the printed matter was printed at a speed of 3 m/min under an air-cooled high-pressure mercury lamp with an output of 80 H/es. The ink was cured by passing through it, and a blue color filter was obtained.

[Evaluation of color filter]

As a result of taking a spectrum of the color filter obtained above, there was a peak wavelength at 456 nm, and the transmittance was 80%.

In addition, dye lake (B) elution and discoloration tests were conducted in the same manner as in Example 1, but these were not observed.

Example 3 [Preparation of colorant] 10 g of Red 14P (manufactured by Nippon Kayaku@) was placed in a 100 cc Erlenmeyer flask, 1 oc of isopropyl alcohol and 10 cc of toluene were added, and the mixture was stirred at room temperature for 30 minutes to dissolve.

To this, tetradecyldimethylbenzyl ammonium chloride and ssan cation M2-100. (Made by Nippon Oil & Fats)
After adding 10 g of , the mixture was heated and stirred at 80° C. for 5 hours to react.

After that, the reaction mixture was allowed to cool to room temperature, and 50 cc of distilled water was added to wash the reaction product.
The pressure was reduced to mtnHg and the mixture was dried at 50° C. for 4 hours to obtain 15.5 g of dye lake (C) paste.

When the particles of this dye lake (C) were observed under an electron microscope, the particle size was 0.5 μm or less.

[Preparation of ink]

The following compound was kneaded using three rolls to produce an ultraviolet curable red ink.

Dye lake (C) obtained above 15 parts by weight Epoxy acrylate 45 parts by weight (Lipoxy 5P-1509, manufactured by Showa Kobunshi ■) Oligoester acrylate 33 parts by weight (Alonisox M-8030, manufactured by Toagosei ■) Silica (Aerosil Ii) 200.5 parts by weight Nippon Aerosil Co., Ltd.) 2.2-dimethoxy-2-phenyl 5 parts by weight Acetophenone (Irgacure 651, manufactured by Ciba Geigy) t-butylhydroquinone 0.1 parts by weight 1 part by weight
00.1 parts by weight [Preparation of color filter] The above ink was printed on a glass plate in the same manner as in Example 1, and the printed matter was heated under an air-cooled high-pressure mercury lamp with an output of 80 W/cm.
The ink was cured by passing at a speed of 3 m/min to obtain a red color filter.

[Evaluation of color filter]

As a result of taking a spectrum of the color filter obtained above, the transmittance at a wavelength of 610 nm was 85%.

Further, the elution and discoloration tests of the dye lake (C) were conducted in the same manner as in Example 1, but these were not observed.

Effects of the Invention According to the present invention, it is possible to provide an ink for color filters using a product obtained by reacting an anionic dye having an organic acid group with an organic compound having a cationic group as a colorant. The color filter used can produce clear colors in response to the transmitted light.

Furthermore, since the ink of the present invention uses a colorant in which an anionic dye is modified with an organic compound having a cationic group, it can be used even when an oil-soluble vehicle is used, such as in lithographic ink. It can be blended well,
The coating properties and coloring properties can be improved.

Further, when a color filter formed using the ink of the present invention is used in a colored display board, the display board can exhibit a display function with excellent color transparency.

In particular, when a coating film of this ink is used for a color filter of a liquid crystal panel such as a liquid crystal color television, the colors can be displayed clearly and an excellent image can be obtained. At this time, the resin component of the coating film is polyester-amino resin,
When UV-curable or electron beam-curable resins are used, they have excellent heat resistance, so they do not deteriorate when exposed to high heat for long periods of time due to sputtering, etc., such as when forming electrodes on this coating. It is possible to avoid the yellowing caused by yellowing, and it is possible to display stably without impairing the original color development.

Claims (5)

[Claims] (1) An ink for color filters containing, as a colorant, a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group. (2) A colored display board characterized by having a colored coating film containing a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group as a coloring agent. (3) A liquid crystal display panel characterized in that a colored coating film containing a reaction product of an anionic dye having an organic acid group and an organic compound having a cationic group as a colorant is used as a color filter for a liquid crystal display. (4) The liquid crystal display panel according to claim 3, wherein the colored coating film contains a polyester-amino resin or an ultraviolet curable resin. (5) The liquid crystal display panel according to claim 3, wherein the colorant is a particle having a particle size of 0.5 μm or less.