JP2001042117A - Green colored composition for color filter and color filter and liquid crystal display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a green color filter having both high transmittance and high color purity while maintaining good fluidity characteristics of the green colored composition and to provide a color filter having improved color characteristics by preparing the pigment from a specified pigment green and a specified pigment yellow. SOLUTION: The pigment is prepared from at least pigment green PG-36 and pigment yellow-PY-138. By using the pigment yellow-PY-138, a color film of high contrast can be obtained by microprocessing such as a salt milling method. Therefore, by preparing the pigment in a fine state having 35 to 120 m2.g-1 specific surface area, preferably 50 to 100 m2.g-1, the green color composition obtains good dispersion stability and the obtained green color film has high contrast. The content ratio of the pigment green PG-36 to the pigment yellow PY-138 is preferably 8:2 to 4:6, and more preferably 7:3 to 6:4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a green coloring composition for a color filter, a color filter using the same, and a liquid crystal display device.

[0002]

2. Description of the Related Art At present, a pigment dispersion method is mainly used for producing a color filter used in a liquid crystal display device or the like. Examples of the pigment dispersion method include a photosensitive acrylic method and a non-photosensitive polyimide method.

[0003] A TFT (thin film transistor) color liquid crystal display, which has been widely used at present, includes a panel in which liquid crystal is sealed between a transparent glass substrate on which a color filter is formed, a transparent glass substrate on which a TFT is formed, and a backlight. The light source is called a light source. When light emitted from the backlight passes through the liquid crystal panel, an image is displayed by controlling the transmittance of the light by the voltage applied to the liquid crystal. Since each pixel needs to be similar to the chromaticity characteristics of the CRT phosphor, the pigment is selected to match the light transmission characteristics of the backlight and the liquid crystal display element, and two or more pigments are adjusted at a fixed ratio. Often used in color.

For example, in a green coloring composition for forming a green coloring film of a color filter, a combination of a green pigment and a yellow pigment is used as a pigment.

Conventionally, Pigment Green PG-36 has been used as a green pigment, and Pigment Yellow P has been used as a yellow pigment.
Y-83 or Pigment Yellow PY-139 has been used. The green color film of the color filter is PG-
By changing the mixing ratio of 36 to PY-83 or PY-139, the color is adjusted to meet the required color characteristics.

More recently, for example, Japanese Patent Application Laid-Open No. H10-16
As described in JP-A-0928, a green pigment is Pigment Green PG-36, and a yellow pigment is Pigment Yellow PY-1.
50 and / or Pigment Yellow PY-185 so as to meet the required color characteristics.

However, the conventional coloring composition for a color filter, regardless of the photosensitive acrylic method or the non-photosensitive polyimide method, has a high transmittance and a high color purity satisfying the color characteristics required for a liquid crystal display device. It was difficult to provide a compatible green colored film.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art. It is an object of the present invention to provide a liquid crystal display device which maintains the flow characteristics of a green colored composition in good condition. Another object of the present invention is to provide a green coloring composition for a color filter which provides a green coloring film having both high transmittance and high color purity by effectively utilizing the bright line of the backlight.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
In a green color composition for a color filter containing a pigment, a polymer, and a solvent as main components, the pigment is at least composed of Pigment Green PG-36 and Pigment Yellow PY-138. Achieved by a green coloring composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention comprises a green color composition for a color filter containing Pigment Green PG-36 and Pigment Yellow PY-138 as pigments.

The constitution of the present invention is effective regardless of the pigment dispersion method in general, that is, regardless of the photosensitive acrylic method and the non-photosensitive polyimide method.

In order to obtain a green colored film having color characteristics satisfying both high transmittance and high color purity, Japanese Patent Application Laid-Open No. H10-16092 has been proposed.
As described in No. 8, Pigment Green PG-3 is used as a green pigment.
6. Pigment yellow PY-150 and / or yellow pigment
Alternatively, it can also be achieved by using Pigment Yellow PY-185.

However, according to the present invention, pigments such as Pigment Green PG-36 and Pigment Yellow PY are used.
A green colored film obtained from a green colored composition for a color filter containing -138 can obtain color characteristics equal to or better than the green colored film. Furthermore, Pigment Yellow PY-138 also has the effect of reducing the birefringence (Δn) of the colored film. In particular, when polyimide having high birefringence is used for the resin of the colored film, the effect is even greater. Become.

If the birefringence of the pixel of the color filter is large, the contrast of the liquid crystal display device when viewed obliquely from side to side differs between the left and right sides, which may cause various display problems. In particular, this tendency becomes more prominent in a liquid crystal display device using a viewing angle enlargement technique. Therefore, the smaller the birefringence index of the pixel is, the better.

Pigment Yellow P used in the present invention
When Y-138 is finely processed by salt milling or the like,
A colored film with high contrast can be obtained. However, when the pigment is too finely divided, the dispersion stability of a green colored composition is deteriorated.

Therefore, the specific surface area of the pigment is 35 m ² · g
Range of ^{-1 ~120m 2} · g ^-1, preferably 40m ² · g ^-1 ~
110 m ² · g ^-1 , more preferably 50 m ² · g ^-1
When the fineness is reduced so as to fall within the range of 100 m ² · g ⁻¹ , the dispersion stability of the green coloring composition using the pigment is good, and a green coloring film with high contrast can be obtained.

In the case of a green colored film, a PY that has not been finely processed
The contrast in a green colored film using -138 is 500 to
In contrast to 600, the contrast of the green colored film using the finely processed PY-138 is 900 to 1100.

The salt milling will be specifically described. A small amount of a water-soluble organic solvent (B) is added as a lubricant to a mixture of an organic pigment and a water-soluble inorganic salt (A), and the mixture is kneaded vigorously with a kneader or the like. Stir to form a slurry. Next, the slurry is filtered, washed with water, and dried if necessary, to obtain a finely divided pigment. Further, by using a resin (C) which is at least partially soluble in the organic solvent (B) at the time of salt milling, a treated pigment which is finer and has less aggregation of the pigment when dried can be obtained.

The inorganic salt (A) used here is not particularly limited as long as it is water-soluble, but it is preferable to use salt (sodium chloride) from the viewpoint of cost. Regarding the mixing ratio between the inorganic salt and the pigment, the higher the ratio of the inorganic salt to the pigment, the higher the fineness efficiency, but the smaller the processing amount of the pigment at one time. Therefore, it is necessary to determine the ratio in terms of both processing efficiency and production efficiency, but it is preferable to use the inorganic salt in a weight ratio of 1 to 10 times the pigment.

The organic solvent (B) is not particularly limited as long as it is water-soluble and does not dissolve the inorganic salt (A).
Since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent is preferred from the viewpoint of safety.
For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2-
(Hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl glycol, diethylene glycol monobutyl ether, triethylene glycol,
Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol and the like are used. Can be

The resin (C) is preferably solid at room temperature,
It must be water-insoluble and at least partly soluble in a water-soluble organic solvent (B) used as a lubricant during salt milling, and may be a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin. Resin or the like is used. Rosin is typical as a natural resin, and rosin derivatives, cellulose derivatives, rubber derivatives, protein derivatives and oligomers thereof are mentioned as modified natural resins. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of the synthetic resin modified with a natural resin include a rosin-modified maleic resin, a rosin-modified phenol resin, and the like.

In order to satisfy the color characteristics required for a liquid crystal display device, it is important to adjust the content ratio of Pigment Green PG-36 and Pigment Yellow PY-138 to perform toning.

The content ratio of Pigment Green PG-36 to Pigment Yellow PY-138 is 8: 2 to 4:
6 is preferable, and more preferably, it is 7: 3 to 6: 4.

On the chromaticity diagram, when the amount ratio of the yellow pigment, Pigment Yellow PY-138, increases, the chromaticity of the green colored film moves in the direction of increasing x, and conversely, decreases when the amount decreases. Move in the direction. Here, x is an index representing the yellow tint of the green coloring film.

In order to satisfy the required color characteristics,
The amount ratio of CI Pigment Yellow PY-138 is 20 to 60% by weight, preferably 25 to 50% by weight, and more preferably 30 to 40% by weight.

In the present invention, other green pigments and yellow pigments may be added as long as the color characteristics are not impaired. As an example of another typical green pigment, Pigment Green (PG-)
7, 10, 47 and the like. Examples of yellow pigments include Pigment Yellow (PY-) 12, 13, 17, 2
0, 24, 83, 86, 93, 94, 95, 109, 1
10, 125, 137, 139, 147, 148, 15
3, 154, 166, 173, 185 and the like. In the present invention, various pigments can be used without being limited to these.

In particular, when a small amount of pigment yellow (PY-) 17, 83, 139, 150, or 185 is added as a yellow pigment, the film thickness can be reduced and a colored film having the same chromaticity can be formed. From the viewpoint of color characteristics, it is preferable to add Pigment Yellow PY-17, 150, 185,
Further, Pigment Yellow PY-150 is more preferably added. Pigment Yellow PY-1
By adding 50 or the like, the viscosity stability of the coloring composition is improved.

If the addition amount of these yellow pigments is too large, the color characteristics will deteriorate, and further, the addition amount of Pigment Yellow PY-138 will decrease in order to match the chromaticity of the coloring film. The refractive index (Δn) increases. Therefore, when a yellow pigment such as Pigment Yellow PY-150 is added, the addition amount is 1 to 20% by weight, preferably 2 to 18% by weight, and more preferably 3 to 15% by weight.

If necessary, the pigment may be one which has been subjected to a surface treatment such as a rosin treatment, an acid group treatment, a basic group treatment, and a pigment derivative treatment.

The resin contained in the colored film of the color filter in the present invention includes acrylic resin, alkyd resin, polyester, polyimide, polyurethane, polyamideimide, polyamide and the like.

Polyimide and polyamide are more preferable than acrylic resin from the viewpoint of heat resistance of the pixel, and polyimide is more preferable than polyamide from the viewpoint of processability of the pixel and dispersion stability of the color paste. Can be

The polyimide in the present invention is a precursor thereof, and is obtained by heating a polyamic acid having a structural unit represented by the general formula (1) as a main component or heating with an appropriate catalyst to form an imide ring or other cyclic structure. Is a polymer formed. As the polyimide precursor, an ester compound thereof is usually used in addition to the polyamic acid.

The polymer has a weight average molecular weight of 500.
Refers to a polymer of 0 or more. Adjustment of the molecular weight is carried out by excessing either the acid or diamine component or by adding a monofunctional acid or amine component. Monocarboxylic acids, carboxylic dianhydrides, monoamines are used as examples of monofunctional acid or amine components. Specific examples include, but are not limited to, benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, aniline, and the like.

[0034]

Embedded image

In the general formula (1), R ¹ represents a tetracarboxylic acid residue, and R ² represents a diamine residue.

Examples of acid dianhydrides are 3,3 ', 4,4
'-Benzophenonetetracarboxylic dianhydride 3,3
', 4,4'-biphenyltrifluropropanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ", 4,4" -parata-phenyltetracarboxylic dianhydride, 3,3 ", 4,4"-
Meta-phenyltetracarboxylic dianhydride, 4,4 '
-(Hexafluoroisopropylidene) diphthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3 1,5-Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexenetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a , 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-
3-furanyl) -naphtho [1,2-C] furan-1,3-
Examples include, but are not limited to, diones.

Examples of diamines include 4,4'-diaminodiphenylsulfone, 3,3 '-(or 4,4') diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 2,5-diaminotoluene, o -Tolidine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, Bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (4
-Aminophenoxy) phenyl] hexafluoropropane 1,3- (or 1,4) diaminocyclohexane,
4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 ´-
Examples include, but are not limited to, diaminodiphenyl ether.

Further, in order to improve the adhesion to the substrate, a diamine component is used as long as the heat resistance is not reduced.
Bis (3-aminopropyl) tetramethyldisiloxane having a siloxane structure may be copolymerized. The siloxane diamine is usually used in an amount of 1 to 20 mol% of the total diamine. If the amount of siloxane diamine is too small, the effect of improving the adhesiveness will not be exhibited, and if it is too large, the heat resistance will decrease. The present invention is not limited to these, and one or more siloxane diamines may be used.

These polyamic acids are synthesized by a known method, that is, by selectively combining tetracarboxylic dianhydride and diamine and reacting them in a solvent.
Usually, amide-based polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and lactone-based polar solvents can be used as a solvent for the synthesis of polyamic acid. . Examples of the solvent other than lactones include methylcellosolve, ethylcellosolve, methylcarbitol, ethylcarbitol and the like in addition to the amide-based polar solvent.

Lactones are aliphatic cyclic esters and compounds having 3 to 12 carbon atoms. As specific examples, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-
Examples include, but are not limited to, caprolactone. Particularly, γ-butyrolactone is preferred in view of the solubility of the polyamic acid.

In the coloring paste used to form the coloring layer of the color filter of the present invention, the polyamic acid and the pigment (or light-shielding agent) are usually in a weight ratio of 1: 9 to 1: 9.
9: 1, preferably 2: 8 to 8: 2, more preferably 3: 7 to 7: 3. If the amount of the polyamic acid is too small, the adhesion between the colored film and the substrate becomes poor, and if the amount of the pigment is too small, the degree of coloring becomes a problem. In addition, in the paste, from the viewpoint of coatability, drying property, etc., the solid content concentration of the polyamic acid and the pigment is 2 to 30%, preferably 3 to 25%, more preferably 5 to 20%. Use in range.

These pigments are mixed with a polyamic acid solution to obtain a coloring liquid. In this case, the pigment may be dispersed in the polyamic acid solution, or the pigment may be dispersed in a solvent in advance and then mixed with the polyamic acid solution. Regarding the selection of these production methods, it is preferable to select an appropriate one depending on the type of the pigment. The method of dispersing the pigment is not particularly limited, and various methods such as a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill can be used.

There is no particular limitation on the solvent used for the coloring paste. Water and common organic solvents can be used. When polyimide is used as a component of the pixel matrix, the solvent used for the coloring paste is preferably a solvent that dissolves polyamic acid. Examples of the solvent for dissolving the polyamic acid include amides such as N, N-dimethylacetamide, N, N-dimethylformamide, and γ.
Lactones such as -butyllactone, 2-pyrrolidone,
And polar organic solvents such as pyrrolidones such as N-methyl-2-pyrrolidone. Usually, it does not dissolve polyamic acid alone, ethanol, butanol, alcohols such as isopropanol, methylcellosolve,
An organic solvent such as cellosolves such as ethyl cellosolve and propylene glycol derivatives such as propylene glycol monomethyl ether can be mixed with a solvent that dissolves polyamic acid.

To the paste of the present invention, a surfactant is added to the paste of the present invention for the purpose of improving applicability, drying property of the colored film, or improving dispersibility of the pigment (or light-shielding agent). You can also. The amount of the surfactant added is usually 0.001 to 10% by weight of the pigment, preferably 0.1 to 10% by weight.
0.01 to 1% by weight. If the addition amount is too small, the coating properties,
There is no effect of improving the drying property of the colored film or the dispersibility of the pigment. If the amount is too large, on the contrary, the coating property becomes poor or the pigment aggregates. Specific examples of the surfactant include ammonium lauryl sulfate, anionic surfactant such as polyoxyethylene alkyl ether triethanolamine sulfate, stearylamine acetate, cationic surfactant such as lauryl trimethyl ammonium chloride, lauryl dimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Nonionic surfactants such as sorbitan monostearate and the like can be mentioned. In the present invention, without being limited to these,
One or more surfactants can be used.
The surfactant can be added at any time during or before or after the pigment dispersion step. However, care must be taken since the dispersibility of the pigment may change depending on the time of addition.

Next, an example of a method of manufacturing and using the color filter of the present invention will be described. For example, a green colored coating film is formed on a substrate with a coloring liquid composed of a polyimide precursor and a pigment. As the substrate, soda glass, alkali-free glass, borosilicate glass, quartz glass, or the like is generally used, but is not limited thereto. Coating is performed by a method such as spinner, spray coating, dipping, roll coating, bar coating, and die coating. Drying is preferably performed in the range of 50 to 180 ° C. for several seconds to several hours using an oven, a hot plate, and infrared rays. A photoresist for pattern formation is applied thereon to form a photoresist layer. Subsequently, using an exposure apparatus, a mask is placed on the photoresist layer coating film, and is exposed to actinic radiation. Examples of the actinic ray include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays and visible rays are preferred. In the case of using a positive photoresist, after exposure, the development of the photoresist layer and the etching of the colored coating film of the polyimide precursor are simultaneously performed with the developer of the positive photoresist. After the etching, the unnecessary photoresist layer is removed. Usually, a solvent such as acetone or cellosolve is used for peeling. The colored film of the polyimide precursor is heat-treated to complete the patterning of the green colored film. The heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and gradually increasing the temperature or selecting a certain temperature range and continuously increasing the temperature. The maximum temperature of this heat treatment is 180 to 400 ° C, preferably 180 to 350 ° C. For example,
Heat treatment is performed at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes each. Alternatively, the temperature may be raised linearly from room temperature to 300 ° C. over 2 hours.

The above steps are repeated for the red and blue pixels and, if necessary, for the black matrix (black). A color filter can be formed by forming an overcoat film made of an acrylic polymer, polysiloxane, polyimide, or the like as necessary, and sputtering a metal oxide film such as ITO.

In the liquid crystal display device of the present invention, it is preferable to use the color filter of the present invention.

An example of a method for manufacturing and using the liquid crystal display device of the present invention will be described. After washing the substrate on which the TFT array is formed on glass, an alignment film is applied and heated. Thereafter, a spherical spacer having a diameter of 5.5 μm was sprayed thereon, superposed on the color filter substrate, and heated at 160 ° C. for 90 minutes while pressurizing in an oven to cure the sealant. After injecting liquid crystal into this cell, the liquid crystal injection port was sealed with an ultraviolet curable resin. Next, the polarizing plate is placed in the cell 2
The liquid crystal display device was completed by attaching the obtained cell to the outside of a glass substrate and further modularizing the obtained cell.

In the liquid crystal display device of the present invention, the combination of the color filter and the backlight makes it possible to provide a wide color reproducibility and perform a bright display.

[0050]

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The measuring method in the examples is as follows.

<Specific Surface Area> Using a high-precision fully automatic gas adsorption apparatus “BELSORP 36” manufactured by Bell Japan Co., Ltd.
After degassing pretreatment at 00 ° C., the adsorption isotherm of N ₂ , 77K was measured. The specific surface area was determined by applying the BET multilayer adsorption theory to the isotherm.

<Viscosity and yield value> R5, manufactured by Toki Sangyo Co., Ltd.
It was measured with a 00 type viscometer. From the ratio of shear stress (s) to shear rate (D), yield value (Sc) is Casso.
It was determined from n plots (formula (1)). √s = √Sc + √ηcD (1) Here, ηc represents Casson viscosity.

<Chromaticity> MCPD20 manufactured by Otsuka Electronics Co., Ltd.
It was measured at 00.

<Thickness> Surfcom 1 manufactured by Tokyo Seimitsu Co., Ltd.
It measured at 500A.

<Birefringence (Δn)> Refractive index nTE, nTM
Is a Metricon prism coupler measuring device PC-20
00 and measured at 540 nm, from which the birefringence (△
n) was calculated. nTE: Refractive index in the TE direction (direction parallel to the film surface) of the thin film nTM: Refractive index in the TM direction (direction perpendicular to the film surface) of the thin film Birefringence Δn = nTE-nTM Raw material of polyamic acid in Examples and The solvents are as follows. BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride PMDA: pyromellitic dianhydride DAE: diaminodiphenyl ether DDS: 3,3'-diaminodiphenyl sulfone SiDA: bis-3- (Aminopropyl) tetramethylsiloxane MA: maleic anhydride NMP: N-methyl-2-pyrrolidone γ-BL: γ-butyrolactone MMB: 3-methyl-3-methoxybutanol (Synthesis of polyamic acid solution) Reference Example 1 Thermometer DAE 1 in a reaction vessel equipped with a dry nitrogen inlet, a heating / cooling device using hot / cooling water, and a stirring device.
50.0 g (0.75 mol), DDS 49.6 g (0.20 mol), SiDA
12.4 g (0.05 mol) was charged together with 2730 g of γ-BL, and BT
After adding 161.0 g (0.50 mol) of DA and 106.8 g (0.49 mol) of PMDA and reacting at 60 ° C. for 5 hours, 1.96 g (0.02 mol) of MA was added.
mol), and further reacted at 60 ° C. for 1 hour. Then, a 15% polyamic acid solution (P) having a viscosity of 15 poise (25 ° C.) was added.
I-1) was obtained. (Refining by Pigment Yellow PY-138 by Salt Milling) Reference Example 2 250.0 g of PY-138 (specific surface area: 27 m ² · g ⁻¹ ), 700 g of sodium chloride, 107 g of rosin-modified maleic resin,
And 160 g of polyethylene glycol, and kneaded with a three-roll mill for 1 hour. Next, add about 3 L of this mixture.
Into a warm water and stirred at 80 ° C. for 1 hour with a high-speed mixer to form a slurry, then filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a 60 ° C. hot air oven for 24 hours. Thus, a treated pigment PY-138 (A) was obtained. PY-138 obtained
The specific surface area of (A) was 41 m ² · g ^-1 .

Reference Example 3 250.0 g of PY-138 (specific surface area: 27 m ² · g ⁻¹ ), 700 g of sodium chloride, 107 g of rosin-modified maleic resin,
And 160 g of polyethylene glycol, and kneaded with a three-roll mill for 3 hours. Next, add about 3 L of this mixture.
Into a warm water and stirred at 80 ° C. for 1 hour with a high-speed mixer to form a slurry, then filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a 60 ° C. hot air oven for 24 hours. Thus, a treated pigment PY-138 (B) was obtained. PY-138 obtained
The specific surface area of (B) was 84 m ² · g ^-1 .

Reference Example 4 250.0 g of PY-138 (specific surface area: 27 m ² · g ⁻¹ ), 700 g of sodium chloride, 107 g of rosin-modified maleic resin,
And 160 g of polyethylene glycol, and kneaded with a three-roll mill for 5 hours. Next, add about 3 L of this mixture.
Into a warm water and stirred at 80 ° C. for 1 hour with a high-speed mixer to form a slurry, then filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a 60 ° C. hot air oven for 24 hours. Thus, a treated pigment PY-138 (C) was obtained. PY-138 obtained
The specific surface area of (C) was 112 m ² · g ⁻¹ .

Reference Example 5 250.0 g of PY-138 (specific surface area: 27 m ² · g ⁻¹ ), 700 g of sodium chloride, 107 g of rosin-modified maleic resin,
And 160 g of polyethylene glycol, and kneaded with a three-roll mill for 8 hours. Next, add about 3 L of this mixture.
Into a warm water and stirred at 80 ° C. for 1 hour with a high-speed mixer to form a slurry, then filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a 60 ° C. hot air oven for 24 hours. Thus, a treated pigment PY-138 (D) was obtained. PY-138 obtained
The specific surface area of (D) was 124 m ² · g ^-1 .

(Formation and Evaluation of Green Colored Film) Example 1 56.0 g of PG-36, 24.0 g of PY-138 and γ-BL 9
20.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours to obtain an 8% dispersion (GD-1). Dispersion (GD-1) 112.5g
And 67.5 g of polyamic acid solution (PI-1)
A solution diluted with 86.7 g and 33.3 g of MMB was added and mixed.
Pigment / polymer ratio: 47/53 green colored paste (G
P-1) was adjusted. Green colored paste (GP-1)
Is spin-coated on a transparent substrate so that the chromaticity after film curing becomes y = 0.580, dried in an air at 120 ° C. for 20 minutes using an oven, and then dried at 280 ° C. for 40 minutes using an oven. The film was cured in the air to form a green colored film.

Example 2 48.0 g of PG-36, 32.0 g of PY-138 and γ-BL 9
20.0 g was charged together with 1500 g of zirconia beads, and dispersed at 4200 rpm for 3 hours using a mill type disperser to obtain an 8% dispersion (GD-2). Green color paste (GP-2) having a pigment / polymer ratio of 47/53 in the same manner as in Example 1.
Was adjusted to form a green colored film.

Example 3 48.0 g of PG-36, 32.0 g of PY-138 (A) and γ-B
L was mixed with 1500 g of zirconia beads, and dispersed with a mill-type disperser at 4200 rpm for 3 hours.
% Dispersion (GD-3) was obtained. A green colored paste (GP: 47/53) having a pigment / polymer ratio of 47/53 in the same manner as in Example 1.
-3) was adjusted to form a green colored film.

Example 4 48.0 g of PG-36, 32.0 g of PY-138 (B) and γ-B
L was mixed with 1500 g of zirconia beads, and dispersed with a mill-type disperser at 4200 rpm for 3 hours.
% Dispersion (GD-4) was obtained. A green colored paste (GP: 47/53) having a pigment / polymer ratio of 47/53 in the same manner as in Example 1.
-4) was adjusted to form a green colored film.

Example 5 48.0 g of PG-36, 32.0 g of PY-138 (C) and γ-B
L was mixed with 1500 g of zirconia beads, and dispersed with a mill-type disperser at 4200 rpm for 3 hours.
% Dispersion (GD-5) was obtained. A green colored paste (GP: 47/53) having a pigment / polymer ratio of 47/53 in the same manner as in Example 1.
-5) was adjusted to form a green colored film.

Example 6 48.0 g of PG-36, 32.0 g of PY-138 (D) and γ-B
L was mixed with 1500 g of zirconia beads, and dispersed with a mill-type disperser at 4200 rpm for 3 hours.
% Dispersion (GD-6) was obtained. A green colored paste (GP: 47/53) having a pigment / polymer ratio of 47/53 in the same manner as in Example 1.
-6) was adjusted to form a green colored film.

Example 7 48.0 g of PG-36, 24.0 g of PY-138 (B),
150 8.0 g and γ-BL920.0 g were zirconia beads 15
The mixture was charged together with 00g, and dispersed at 4200 rpm for 3 hours using a mill-type disperser to obtain an 8% dispersion (GD-7). A green coloring paste (GP-7) having a pigment / polymer ratio of 47/53 was prepared in the same manner as in Example 1 to form a green coloring film.

Example 8 48.0 g of PG-36, 16.0 g of PY-138 (B),
150 16.0 g and γ-BL920.0 g were zirconia beads 1
The mixture was charged together with 500 g, and dispersed at 4200 rpm for 3 hours using a mill type disperser to obtain an 8% dispersion (GD-8). A green colored paste (GP-8) having a pigment / polymer ratio of 47/53 was prepared in the same manner as in Example 1 to form a green colored film.

Comparative Example 1 PG-36 70.4 g, PY-83 9.6 g and γ-BL 920.
0 g together with 1500 g of zirconia beads was dispersed with a mill type disperser at 4200 rpm for 3 hours to obtain an 8% dispersion (GD-9). A green colored paste (GP-9) having a pigment / polymer ratio of 47/53 was prepared in the same manner as in Example 1 to form a green colored film.

Comparative Example 2 70.4 g of PG-36, 9.6 g of PY-139 and γ-BL 92
0.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours to obtain an 8% dispersion (GD-10). Green colored paste (GP-1) having a pigment / polymer ratio of 47/53 in the same manner as in Example 1.
0) was adjusted to form a green colored film.

As described above, the viscosities, yield values, and frozen (−25) of the pastes (GP-1 to 10) of Examples 1 to 8 and Comparative Examples 1 and 2 were obtained.
Table 1 shows the rate of increase in viscosity after 3 months. Table 2 shows the chromaticity, contrast, film thickness, and birefringence (Δn) of the formed green colored film.

[0070]

[Table 1]

[0071]

[Table 2]

Pigment Yellow PY-138 as the yellow pigment
By using, a green colored film brighter than the conventional one could be obtained. Further, as the content of Pigment Yellow PY-138 increases, the birefringence decreases, so that a colored film having low birefringence could be obtained at the same time. Pigment Yellow PY-138 (A) having a large specific surface area in place of Pigment Yellow PY-138,
By using (B), (C) and (D), a green colored film having high contrast could be obtained. As the fine dispersion is advanced, the contrast becomes higher, but the viscosity stability of the green coloring composition becomes worse. When the specific surface area became 120 m ² · g ⁻¹ or more, the flow characteristics and the storage stability became unusable levels. Pigment Green PG-36 and Pigment Yellow PY-138
By adding -150, the thickness of the green colored film could be reduced without significantly lowering the color characteristics, and the flow characteristics and the storage stability of the green colored composition could be improved.

(Preparation of Color Filter and Preparation of Liquid Crystal Display) Example 9 A green coloring composition (0.7 mm thick) was formed on an alkali-free glass substrate (0.7 mm thick) on which a resin black matrix pattern having a thickness of 1.0 μm was formed. GP-4) by spin coating at 50 ° C.
For 10 minutes, at 90 ° C. for 10 minutes, and at 110 ° C. for 20 minutes using an oven and dried in air using an oven.
To obtain a polyimide precursor colored film. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Co., Ltd.) was applied on this film, and dried by heating at 80 ° C. for 20 minutes to obtain a 1.1 μm resist film. UV illuminator PLA-5 manufactured by Canon Inc.
Using 01F, an ultraviolet ray having a wavelength of 365 nm and an intensity of 50 mJ / cm ² was irradiated through a chromium photomask. After the exposure, the photoresist and the polyimide precursor colored film were simultaneously developed by immersion in a developer consisting of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. After the edging, the unnecessary photoresist layer was peeled off with methylcellosolve acetate.
Further, the thus obtained polyimide precursor colored film was heat-treated in a nitrogen atmosphere at 300 ° C. for 30 minutes to obtain a 1.2 μm-thick green colored film pattern. Thereafter, in the same manner, each of the blue coloring composition and the red coloring composition,
A pattern having a thickness of 1.2 μm was formed.

After dissolving 65.05 g of trimellitic acid in 280 g of γ-butyl lactone, 74.95 g of γ-aminopropyltriethoxysilane was added and heated at 120 ° C. for 2 hours. To 20 g of the obtained solution, 7 g of bisphenoxyethanol full orange glycidyl ether and 15 g of diethylene glycol dimethyl ether were added, and the mixture was stirred at room temperature (about 23 ° C.) for 2 hours. The obtained resin solution composition was spin-coated on the above color filter, and then heated at 100 ° C. for 5 minutes, 260
By heating at 30 ° C. for 30 minutes, an overcoat having a film thickness of 1.0 μm was obtained. Next, when a film of ITO was formed on the overcoat by a sputtering method,
IT with a surface resistance of 15 Ω / □ at 00 Å
O was obtained. Through the above operation, a color filter having three primary colors of red, green, and blue, and having an overcoat and ITO was obtained.

Further, after the color filter on which the transparent electrode layer is formed is washed with a neutral detergent, an alignment film made of a polyimide resin is applied by a printing method, and is applied with a hot plate.
Heated at 0 ° C. for 10 minutes. The thickness was 0.07 μm. After this, the color filter substrate is rubbed,
The sealant was applied by a dispense method, and heated at 90 ° C. for 10 minutes on a hot plate.

On the other hand, the substrate on which the TFT array is formed on the glass is similarly washed, and then an alignment film is applied and heated. Thereafter, a spherical spacer having a diameter of 5.5 μm was sprayed thereon, superposed on the color filter substrate, and heated at 160 ° C. for 90 minutes while pressurizing in an oven to cure the sealant. After injecting liquid crystal into this cell, the liquid crystal injection port was sealed with an ultraviolet curable resin. Next, a polarizing plate was attached to the outside of the two glass substrates of the cell, and the obtained cell was modularized to complete a liquid crystal display device.
As a result of evaluating the color characteristics of the obtained liquid crystal display device, it was possible to obtain the color characteristics satisfying both high transmission and high color purity.

Example 10 Example 9 except that a green coloring composition (GP-7) was used.
The same operation as described above was performed to complete the liquid crystal display device. As a result of evaluating the color characteristics of the obtained liquid crystal display device, it was possible to obtain the color characteristics that achieve both high transmission and high color purity without any display problems caused by the birefringence.

[0078]

As described above, according to the present invention, a green colored film having both high transmittance and high color purity can be obtained while maintaining good flow characteristics of the green colored composition. As a result, a color filter with improved color characteristics can be obtained, and further, the color characteristics of the liquid crystal display device can be improved.

Claims (9)

[Claims] 1. A green coloring composition for a color filter comprising at least a pigment, a polymer and a solvent, wherein the pigment is at least Pigment Green PG-36.
And a green coloring composition for a color filter, comprising: CI Pigment Yellow PY-138. 2. A Pigment Yellow PY-138 specific surface area of 35m ² · g ^-1 or more ~120m claim 1 color filter for the green coloring composition, wherein a is in the range of ² · g ^-1 of. 3. Pigment Yellow PY-138 in a pigment
3. The green coloring composition for a color filter according to claim 1, wherein the amount ratio is in the range of 20 to 60% by weight. 4. 4. A pigment containing Pigment Yellow PY-150 as a third component in the pigment.
The green coloring composition for a color filter according to any one of the above. 5. A pigment yellow PY-150 in a pigment.
5. The green coloring composition for a color filter according to claim 4, wherein the amount ratio is in the range of 1 to 20% by weight. 6. The green coloring composition for a color filter according to claim 1, wherein the polymer is a resin having a carboxyl group. 7. The green coloring composition for a color filter according to claim 6, wherein the polymer is a polyamic acid. 8. A color filter using the green coloring composition for a color filter according to claim 1. 9. A liquid crystal display device using the color filter according to claim 8.