JP2003227921A - Coloring composition for color filter, color filter using the same, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter with high display quality by forming a colored film with high contrast by optimizing a specific surface area of a yellow pigment. <P>SOLUTION: In a coloring composition for the color filter comprising at least a pigment, a polymer, and a solvent, the coloring composition for the color filter is characterized by having 30 wt.% or higher content of the yellow pigment in the pigment component, further having 70-120 m<SP>2</SP>/g specific surface of the yellow pigment, and having the yellow pigment composed of one or more kinds of yellow pigments selected from a group composed of at least a quinophthalone pigment, an isoindolin pigment, a nickel azo complex pigment, and a methane-azomethine pigment. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a 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 In order to color a liquid crystal display device, three
Primary colors R (red), G (green), B (blue) or Y
A color filter in which pixels of (yellow), M (magenta), and C (cyan) are arranged in a line or a mosaic is used. Currently, the pigment dispersion method is the main method for producing color filters. The pigment dispersion method includes a photosensitive acrylic method and a non-photosensitive polyimide method. A TFT (Thin Film Transistor) color liquid crystal display, which is widely used at present, is called a backlight in which a liquid crystal is enclosed between a transparent glass substrate on which a color filter is formed and a transparent glass substrate on which a TFT is formed. Composed of a light source. When the light emitted from the backlight passes through the liquid crystal panel, its transmittance is controlled by the voltage applied to the liquid crystal to display an image. The pigment of each pixel is selected to match the light transmission characteristics of the backlight and the liquid crystal display element. For example, the R and G pixels are often used by toning two or more kinds of pigments at a fixed ratio. In the case of the R pixel, one or more types of yellow pigment and orange pigment are selected in addition to the red pigment, and the colors are adjusted at a fixed ratio before use. Similarly, for the G pixel, one or more kinds of yellow pigment and orange pigment are selected in addition to the green pigment, and the colors are adjusted at a fixed ratio. It is generally said that yellow pigments have a problem in dispersibility, and relatively large pigment agglomerated particles remaining in pixels due to poor dispersibility scatter and depolarize polarized light, which may lower the contrast of the liquid crystal display device. there were. On the other hand, JP-A-8-295808 and JP-A-8-29
In Japanese Patent No. 5809, it is pointed out that the dispersibility of the coloring composition for R pixels and G pixels to which the yellow pigment is added can be improved by miniaturizing the yellow pigment. In addition, JP-A-9
-197118 examines the relationship between the particle size of the yellow pigment and the contrast of the R pixel, and shows that the finer the yellow pigment, the better the dispersibility and the greater the contrast. In the above example, the finer the yellow pigment, the more G
Although it is shown that the dispersibility of pixels and R pixels is good and the contrast is high, the present inventors investigated in detail the effect of miniaturization of the yellow pigment, and found that the pixel contrast was monotonic with respect to the miniaturization of the yellow pigment. Is not improved to
It was found that there is a saturation point in the improvement of the pixel contrast with respect to the miniaturization of the yellow pigment. Since miniaturization of the yellow pigment requires a great deal of energy and time, it is not preferable to miniaturize it more than necessary. If the micronization is advanced too much, the re-aggregation force may be increased and the contrast may be lowered.

Further, no clear correlation was found in the relationship between the particle size of the pigment observed by TEM and the contrast of the pixel, and it was found that the contrast varies even between the pigments that appear to have the same particle size.

As a result of detailed examination of the relationship between the fineness of the pigment and the contrast of the pixel, the present inventors have found that there is a clear correlation between the specific surface area of the pigment and the contrast, and the ratio within a certain range. It was discovered that the contrast of pixels can be increased by using a pigment having a surface area.

[0005]

The present invention was conceived in view of the above-mentioned drawbacks of the prior art. The object of the present invention is to provide a coloring composition containing a yellow pigment having excellent dispersibility, To create a color filter with high display performance. Another object is to provide a liquid crystal display device having excellent display performance by using a color filter having a large contrast.

[0006]

The object of the present invention is as follows.
In a coloring composition for a color filter composed of at least a pigment, a polymer and a solvent, the content of the yellow pigment in the pigment component is 30% by weight or more, and the specific surface area of the yellow pigment is 70 to 70%. 120 m ² / g, and
The yellow pigment is at least a quinophthalone pigment,
1 selected from the group consisting of isoindoline pigments, nickel azo complex pigments, and methine / azomethine pigments
This is achieved by a coloring composition for a color filter, which is characterized by comprising at least one kind of yellow pigment.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The yellow pigment according to the present invention can be applied to pixels of any color as long as it contains a yellow pigment. However, the coloring composition for G pixels and the coloring for R pixels having a high content of yellow pigment. It is effective for the composition or the coloring composition for Y pixels, and is particularly effective for G pixels in which the amount of yellow pigment added is large. A green pigment and a yellow pigment are mainly used for the G pixel, and the color is adjusted by changing the composition ratio of the green pigment and the yellow pigment so as to match the light transmission characteristics of the backlight. Regarding the color characteristics of the G pixel, the color becomes darker and the color reproducibility becomes higher as the chromaticity y increases. Further, the chromaticity x changes depending on the content of the yellow pigment,
The larger x is, the larger the yellowness is, and the smaller x is, the smaller the yellowness is. In a liquid crystal display device, R pixel, G
The chromaticity (white balance) when the pixels and the B pixels are turned on at the same time and displayed in white is important, and it is necessary to match each pixel with a target chromaticity range.

For example, the G pixel of a color filter used in a liquid crystal display device for a monitor application or a television application must have the chromaticity y of 0.570 or more at the C light source, and the chromaticity x can also be, for example, When y is 0.580, x is 0.2
It is preferably 70 or more, more preferably 0.
In the range of 270 to 0.340, most preferably 0.272
The range is up to 0.320. Also, the Y value that represents the brightness is 5
It is preferably 3 or more, more preferably 53.
It is 5 or more, and most preferably 54.0 or more. Therefore, in order to achieve the desired color characteristics in the G pixel of the present invention, the yellow pigment is preferably added in an amount of 30% by weight or more, and more preferably 30 to 60% of the total pigment components.
% By weight, most preferably 30-55% by weight. If the content is less than 30% by weight, the desired color characteristics of the G pixel cannot be achieved, and the display quality of the color filter and further the display quality of the liquid crystal display device will be degraded.

The yellow pigment of the present invention has a specific surface area of 70 m ² / g.
The above is important. The specific surface area is 70 m ² /
When it is less than g, the contrast of the colored film employing the yellow pigment does not become 800 or more, and the performance of the color filter becomes unsatisfactory. The contrast here is 2
The transmitted light intensity when the measurement object is sandwiched with the polarization directions of the two polarizing plates parallel, divided by the transmitted light intensity when the measurement object is sandwiched with the polarization directions of the two polarizing plates perpendicular. And is also called depolarization. The content of the yellow pigment in all the pigments greatly affects the contrast of the colored film. As the content of the yellow pigment increases, the contrast tends to decrease, but the effect of improving the contrast increases by increasing the specific surface area of the yellow pigment. In the present invention, when the content of the yellow pigment in all the pigments is 30% by weight, the effect of the specific surface area becomes remarkable. On the other hand, the content of yellow pigment is 30
If it is less than wt%, the difference in specific surface area of the yellow pigment does not significantly affect the contrast of the colored film. Further, the effect becomes more remarkable as the content of the yellow pigment increases.

The content of yellow pigment in all pigments is 30 or more and 40
In the range of less than wt%, it is important that the specific surface area is 70 m ² / g or more. Since the contrast is more preferably 1000 or more, the specific surface area is 74 m ² / g
More preferably, it is more preferably 78 m ² / g or more. Further, when the amount ratio of the yellow pigment in the total pigment is 40% by weight or more, the performance of the yellow pigment tends to be more significantly reflected as compared with the case where it is in the range of 30% or more and less than 40% by weight. Is preferably 72 m ² / g or more. Further, the specific surface area is preferably 76 m ² / g or more, and most preferably 80 m ² / g or more.

On the other hand, if the specific surface area is too large, the dispersibility deteriorates, and the re-aggregation of the pigment causes the deterioration of the stability of the dispersion and the deterioration of the contrast. If the specific surface area exceeds 120 m ² / g, the dispersibility will be particularly reduced. Further, it may take a lot of energy and time to miniaturize the pigment, and thus unnecessarily miniaturization is not preferable. Therefore, the specific surface area of the yellow pigment of the present invention is 120 m ²
It is important that it is less than or equal to / g.

The miniaturization of the yellow pigment can be carried out by controlling the synthesis conditions of the yellow pigment and salt milling after the synthesis. The salt milling will be specifically described.
A small amount of a water-soluble organic solvent (B) as a lubricant is added to a mixture of an organic pigment and a water-soluble inorganic salt (A), and the mixture is kneaded strongly with a kneader or the like, and then this mixture is put into water to obtain a high speed mixer. Stir with the same to make a slurry. Next, this slurry is filtered, washed with water, and optionally dried to obtain a finely divided pigment. Further, by using the resin (C) which is at least partially soluble in the organic solvent (B) at the time of salt milling, it is possible to obtain a treated pigment which is finer and has less aggregation of the pigment during drying. 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 of the inorganic salt and the pigment, the higher the amount ratio of the inorganic salt to the pigment, the higher the atomization efficiency,
The amount of pigment to be treated once is reduced. Therefore, it is necessary to determine the amount ratio from both aspects of treatment 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).
The solvent having a high boiling point is preferable from the viewpoint of safety, because the temperature rises during salt milling and the solvent easily evaporates.
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, etc. are used. To be

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

The yellow pigment used in the present invention is a pigment in which the color characteristics of the colored film using the yellow pigment are such that the color characteristics are higher in color purity and higher in transmission, and are excellent in heat resistance and light resistance. It is desirable that the pigment is a quinophthalone pigment and at least one yellow pigment selected from the group consisting of an isoindoline pigment, a nickel azo complex pigment, and a methine / azomethine pigment.

Specific examples include quinophthalone pigments such as Pigment Yellow (PY-) 138. Pigment yellow (PY-) 139 and 185 are mentioned as an isoindoline pigment. Pigment yellow (PY-) as an isoindolinone pigment
109, 110, 173, etc. are raised. Pigment Yellow (PY-) 1 as a nickel azo complex pigment
50, 153, etc. are raised. Pigment Yellow (PY-) 117, 1 as a methine / azomethine pigment
29 is raised.

Among these, pigment yellow (PY
-) 138 can form a colored film having higher color purity and high transmission, and further has an effect of reducing the birefringence (Δn) of the colored film. In particular, polyimide having high birefringence can be more preferably used as a yellow pigment when used as a resin for a colored film.

In the present invention, other yellow pigments may be added as long as the color characteristics are not impaired. As examples of other typical yellow pigments, in addition to the above yellow pigments, pigment yellow (PY-) 12, 13, 17, 20, 24, 83, 8
6, 93, 94, 95, 125, 137, 147, 14
8, 154, 166 and the like. In the present invention, various pigments can be used without being limited thereto.
As the above-mentioned pigment, those which have been subjected to surface treatment such as rosin treatment, acidic group treatment, basic group treatment, pigment derivative treatment and the like may be used if necessary.

Pigment Yellow (PY-) 138 and Pigment Yellow (PY-) 17, 83, 129, 13
By adding a small amount of 9,150,185, a colored film having the same chromaticity can be formed with a thin film thickness. Pigment Yellow (PY) -from the viewpoint of color characteristics, heat resistance, and light resistance.
129, 150 and 185 are preferably added, and more preferably Pigment Yellow (PY) -150 is added. Pigment Yellow (PY)
By adding -150 or the like, the viscosity stability of the coloring composition is improved.

If the amount of these yellow pigments added is too large, the color characteristics deteriorate, and further, Pigment Yellow (PY-) 138.
The birefringence of the colored film (△
n) becomes large. Therefore, Pigment Yellow P
When a yellow pigment such as Y-150 is added, the addition amount thereof is preferably 1 to 25% by weight, more preferably 1 to 20% by weight, and most preferably 1 to 15% by weight, based on all pigments.

Pigment yellow (PY-) 1 for G pixel
When 38 is used, Pigment Green (PG-) 7, 10, 36 and 47 can be used as a green pigment, but Pigment Green (PG-) 36 is used from the viewpoint of color characteristics.
Is preferably used. In order to match the color characteristics of the G pixel with the light transmission characteristics of the backlight and the liquid crystal display element, the content ratio of Pigment Green (PG-36) and Pigment Yellow (PY-) 138 is adjusted to adjust the color. This is very important. In this case, Pigment Yellow (PY
The content of-) 138 is 30% by weight or more, preferably 30 to 60% by weight, and more preferably 35 to 50% by weight based on the total pigment.
% By weight.

Furthermore, by adding Pigment Yellow (PY-) 150 as the third component of the pigment, a colored film having the same chromaticity can be formed with a thin film thickness, and the viscosity stability of the green colored composition can be improved. It is possible to improve the sex. In this case, the content of Pigment Yellow (PY-) 150 is preferably in the range of 1 to 25% by weight, more preferably 1 to 20% by weight, based on the total pigment.
Most preferably, it is in the range of 1 to 15% by weight.

Further, when the G pixel is toned with a green pigment and a yellow pigment, it is preferable to set the specific surface area of the green pigment smaller than the specific surface area of the yellow pigment because the contrast of the G pixel can be increased. Although the detailed mechanism for this is not clear, it is considered that the green pigment acts as a dispersion aid for the yellow pigment, and the smaller the specific surface area of the green pigment, the more effectively the yellow pigment can be finely dispersed. It is estimated to be.
The specific surface area of the green pigment at this time is preferably 56 m ² / g or less, more preferably 50 m ² / g or less, still more preferably 45 m ² / g or less. The specific surface area of the green pigment is 33
It is preferably m ² / g or more.

The yellow pigment of the present invention can also be used in R pixels, and specific examples of the red pigment that can be used at this time are Pigment Red (PR-) 9, 48, 97 and 12
2, 123, 144, 149, 166, 168, 17
7, 180, 190, 192, 215, 216, 21
7, 220, 223, 224, 226, 227, 22
8, 240, 254 and the like. In the present invention, various pigments can be used without being limited thereto.
Pigment Red (PR-) 177, from the viewpoint of color characteristics,
254 is preferably used. As the above-mentioned pigment, those which have been subjected to surface treatment such as rosin treatment, acidic group treatment, basic group treatment, pigment derivative treatment and the like may be used if necessary.

The resin used in the present invention is for holding the pigment in a dispersed state, and is not particularly limited as long as it is a resin used in a coloring composition for a color filter, and any resin can be used. Is. For example, acrylic resin,
Various resins such as alkyd resin, melamine resin, polyester, polyvinyl alcohol, phenol resin, polyimide, polyurethane, polyamide-imide, and polyamide can be used. In particular, a resin that is soluble in an aqueous alkaline solution is desirable because it can simplify the equipment during the development or edging process. Among the resins that dissolve in the alkaline aqueous solution, a resin having a carboxyl group is preferably used, and specifically, an acrylic resin and a polyimide are preferable in terms of solvent resistance. In the case of polyimide, polyimide precursors are more preferable because they function as a dispersant for the pigment. From the viewpoint of heat resistance of the color filter, it is preferable to use polyimide.

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

Here, the polymer has a weight average molecular weight of 500.
It means 0 or more polymers. The adjustment of the molecular weight is carried out by adding either an acid component or a diamine component in excess, 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.

[0028]

[Chemical 1]

In the above general formula (1), R ¹ represents a tetracarboxylic acid residue and R ² represents a diamine residue. Examples of the acid dianhydride include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 3,3 ′, 4,4′-biphenyltrifluforopropane tetracarboxylic acid dianhydride, 2, 3,5-Tricarboxycyclopentylacetic acid 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, One, two, three,
4-cyclobutanetetracarboxylic dianhydride, 1,2,
3,4-cyclopentanetetracarboxylic dianhydride, 1,
2,3,5-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-dione and the like, but are not limited thereto.

Examples of diamines are 4,4'-diaminodiphenyl sulfone, 3,3 '-(or 4,4') diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 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 thereof include, but are not limited to, diaminodiphenyl ether.

Further, in order to improve the adhesiveness with the substrate, as a diamine component, as long as the heat resistance is not deteriorated,
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% based on all diamines. 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, as a solvent for synthesizing polyamic acid, an amide-based polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc., or a lactone-based polar solvent may be mixed and used. . Examples of the solvent other than the lactones include methyl cellosolve, ethyl cellosolve, methyl carbitol, and ethyl carbitol, in addition to the amide polar solvent.

The lactones are aliphatic cyclic esters having 3 to 12 carbon atoms. Specific examples include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-
Examples include, but are not limited to, caprolactone. In particular, γ-butyrolactone is preferable in terms of solubility of polyamic acid.

In the color paste used for forming the color layer of the color filter of the present invention, the polyamic acid and the pigment (or the light shielding agent) are usually 1: 9 by weight.
It is used in a mixture of 9: 1, preferably 2: 8 to 8: 2, and more preferably 3: 7 to 7: 3. If the amount of polyamic acid is too small, the adhesion between the colored coating and the substrate will be poor, and if the amount of pigment is too small, the degree of coloring will be a problem. In addition, in the paste, the solid content concentration of the polyamic acid and the pigment combined is 2 to 30%, preferably 3 to 25%, and more preferably 5 to 20% from the viewpoints of coating properties, drying properties, and the like. Used in the range.

These pigments are mixed with a polyamic acid solution to obtain a colored liquid. In this case, the pigment may be dispersed in the polyamic acid solution, or the pigment may be previously dispersed in a solvent and then mixed with the polyamic acid solution. Regarding the selection of these manufacturing methods, it is preferable to select an appropriate one depending on the kind of 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 above color 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 color paste is preferably a solvent that dissolves polyamic acid. As the solvent for dissolving the polyamic acid, amides such as N, N-dimethylacetamide and N, N-dimethylformamide, γ
-Lactones such as butyrolactone, 2-pyrrolidone,
Examples include polar organic solvents such as pyrrolidones such as N-methyl-2-pyrrolidone. In addition, usually, polyamic acid does not dissolve alone, ethanol, butanol, alcohols such as isopropanol, methyl cellosolve,
An organic solvent such as cellosolves such as ethyl cellosolve and propylene glycol derivatives such as propylene glycol monomethyl ether can be used as a mixture 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 the coating property, the drying property of the colored film, or improving the 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.
It is from 0 to 1% by weight. If the amount added is too small, 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 coatability becomes poor and the pigment aggregates. Specific examples of the surfactant, ammonium lauryl sulfate, anionic surfactants such as polyoxyethylene alkyl ether sulfate triethanolamine, stearylamine acetate, cationic surfactants such as lauryl trimethyl ammonium chloride, lauryl dimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Examples include nonionic surfactants such as sorbitan monostearate. The present invention is not limited to these,
One or more surfactants can be used.
The addition of the surfactant can be carried out at any point during or before the step of dispersing the pigment. However, care must be taken because 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. A 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, etc. are usually used, but the substrate is not limited to these. As the coating, methods such as spinner, spray coating, dipping, roll coating, bar coating and die coating are used. For drying, use an oven, hot plate, and infrared rays.
It is preferable to carry out in the range of up to 180 ° C for several seconds to several hours.
A photoresist for forming a pattern is applied on this to form a photoresist layer. Then, using an exposure device, a mask is placed on the photoresist layer coating film, and actinic rays are irradiated to expose the film. Examples of the actinic rays include ultraviolet rays, visible rays, electron rays and X-rays, and ultraviolet rays and visible rays are preferable. When a positive photoresist is used, after exposure, development of the photoresist layer and etching of the colored coating film of the polyimide precursor are simultaneously performed with a developer for 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 coating film of the polyimide precursor is heat-treated to finish patterning the colored coating 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 1
It is preferable to carry out at 80 to 350 ° C. For example, 130 ℃, 2
Heat treatment is performed at 00 ° C. and 300 ° C. for 30 minutes each. Alternatively, the temperature may be linearly raised from room temperature to 300 ° C. over 2 hours.

The above steps are repeated for the coloring composition of three colors of red, green and blue, or for yellow, cyan, magenta and, if necessary, the black matrix (black). If necessary, an overcoat film made of acrylic polymer, polysiloxane, polyimide or the like is formed, and a metal oxide film such as ITO is sputtered, whereby a color filter can be prepared.

The color filter of the present invention is preferably used in the liquid crystal display device of the present invention. The color filter of the present invention may be formed on either side of a transparent substrate sandwiching a liquid crystal. That is, it can also be adopted in a configuration (color filter on array: COA) in which a color filter is formed on the side of a substrate on which active elements such as TFTs are formed. Further, it can be applied not only to a transmissive liquid crystal display device equipped with a backlight but also to a reflective liquid crystal display device that reflects external light for use.

An example of the method of manufacturing and using the liquid crystal display device of the present invention will be described. After cleaning the substrate having the TFT array formed on the glass, an alignment film is applied and heated. Then, spherical spacers having a diameter of 5.5 μm were scattered, superposed on the color filter substrate, and heated at 160 ° C. for 90 minutes while applying pressure in an oven to cure the sealant. After the liquid crystal was injected into this cell, the liquid crystal injection port was sealed with an ultraviolet curable resin. Next, attach the polarizing plate to the cell 2
The liquid crystal display device was completed by sticking it to the outside of a glass substrate and then modularizing the obtained cells.

The liquid crystal display device of the present invention is used for displaying on a personal computer, a word processor, an engineering workstation, a navigation system, a television, a video, etc., and can also be used as a light modulation element.

In the liquid crystal display device of the present invention, it is possible to perform display with good color characteristics and high contrast. In particular, in a liquid crystal display device for a monitor or a television, the contrast is preferably 400 or more.

[0044]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto. Moreover, the measuring methods in the examples are as follows.

<Specific surface area> Using a high precision fully automatic gas adsorption device "BELSORP36" manufactured by Nippon Bell Co., Ltd., 10
After degassing pretreatment at 0 ° C., adsorption isotherms of N ₂ and 77 K were 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 viscosity shear stress (s) and shear rate (D), the yield value (Sc) is Casso.
It was calculated from n plot (formula (1)). √s = √Sc + √ηcD (1) where ηc represents Casson viscosity.

<Chromaticity>"MCPD2" manufactured by Otsuka Electronics Co., Ltd.
It was measured at 000 ".

<Film Thickness> Measured with "Surfcom 1500A" manufactured by Tokyo Seimitsu Co., Ltd.

<Birefringence (Δn)> Refractive Index nTE, nTM
Is a prism coupler measuring device "PC-2" manufactured by Metricon
The birefringence (Δn) was calculated from the measured value at 000 ″ at 540 nm. NTE: Refractive index in the TE direction of the thin film (direction parallel to the film surface) nTM: TM direction of the thin film (perpendicular to the film surface Direction) Refractive index Birefringence Δn = nTE-nTM The raw materials and solvents for the polyamic acid in the examples are as follows: BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride PMDA: Pyromellitic dianhydride DAE: Diaminodiphenylether DDS: 3,3'-Diaminodiphenylsulfone SiDA: Bis-3- (aminopropyl) tetramethylsiloxane MA: Maleic anhydride NMP: N-Methyl-2-pyrrolidone γ-BL: γ-butyrolactone MMB: 3-methyl-3-methoxybutanol.

A. Synthesis Example 1 of Polyamic Acid Solution DAE 1 was added to a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device with 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 with γ-BL 2730 g, and BT
DA 161.0 g (0.50 mol) and PMDA 106.8 g (0.49 mol) were added, and after reacting at 60 ° C. for 5 hours, MA 1.96 g (0.02 mol)
mol) was added, and the mixture was further reacted at 60 ° C. for 1 hour, and then a 15% polyamic acid solution (P
I-1) was obtained.

B. Pigment Yellow PY-138 refined by salt milling Reference Example 2 PY-138 (A) (specific surface area: 64 m ² / g) 250.0 g,
Sodium chloride 700g, rosin-modified maleic acid resin 107
g and 160 g of polyethylene glycol were charged and kneaded with a three-roll mill for 1 hour. Then add about 3 parts of this mixture.
Pour into warm water of L, stir for 1 hour with a high speed mixer while heating to 80 ° C. to make a slurry, then filter,
It was washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-138 (B). Obtained PY-13
The specific surface area of 8 (B) was 72 m ² / g.

Reference Example 3 PY-138 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 3 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum-dried for 24 hours in a hot air oven at 60 ° C. to prepare pigment PY-138 ( C)
Got The specific surface area of the obtained PY-138 (C) is 77 m.
It was ² / g.

Reference Example 4 Py-138 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 5 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum-dried for 24 hours in a hot air oven at 60 ° C. to prepare pigment PY-138 ( D)
Got The specific surface area of the obtained PY-138 (D) is 85 m.
It was ² / g.

Reference Example 5 PY-138 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 8 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum-dried for 24 hours in a hot air oven at 60 ° C. to prepare pigment PY-138 ( E)
Got The specific surface area of the obtained PY-138 (E) is 107.
It was m ² / g.

Reference Example 6 PY-138 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded for 12 hours with a three-roll mill. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum-dried for 24 hours in a hot air oven at 60 ° C. to prepare pigment PY-138 ( F)
Got The specific surface area of the obtained PY-138 (F) is 126.
It was m ² / g.

C. Pigment Yellow PY-150 refined by salt milling Reference Example 7 PY-150 (A) (specific surface area: 67 m ² / g) 250.0 g,
Sodium chloride 700g, rosin-modified maleic acid resin 107
g and 160 g of polyethylene glycol were charged and kneaded with a three-roll mill for 1 hour. Then add about 3 parts of this mixture.
Pour into warm water of L, stir for 1 hour with a high speed mixer while heating to 80 ° C. to make a slurry, then filter,
It was washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-150 (B). The obtained PY-15
The specific surface area of 0 (B) was 72 m ² / g.

Reference Example 8 250.0 g of PY-150 (A), 700 g of sodium chloride, 107 g of rosin-modified maleic acid resin, and 160 g of polyethylene glycol were charged and kneaded for 3 hours with a three-roll mill. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-150 ( C)
Got The specific surface area of the obtained PY-150 (C) is 78 m.
It was ² / g.

Reference Example 9 PY-150 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 5 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-150 ( D)
Got The specific surface area of the obtained PY-150 (D) is 84 m.
It was ² / g.

Reference Example 10 PY-150 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 8 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-150 ( E)
Got The specific surface area of the obtained PY-150 (E) is 90 m.
It was ² / g.

D. Pigment Yellow PY-129 refined by salt milling Reference Example 11 PY-129 (A) (specific surface area: 65 m ² / g) 250.0 g,
Sodium chloride 700g, rosin-modified maleic acid resin 107
g and 160 g of polyethylene glycol were charged and kneaded with a three-roll mill for 1 hour. Then add about 3 parts of this mixture.
Pour into warm water of L, stir for 1 hour with a high speed mixer while heating to 80 ° C. to make a slurry, then filter,
It was washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-129 (B). Obtained PY-12
The specific surface area of 9 (B) was 73 m ² / g.

Reference Example 12 PY-129 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 3 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, filtration, washing with water to remove sodium chloride and polyethylene glycol, and vacuum drying in a hot air oven at 60 ° C. for 24 hours to obtain treated pigment PY-129 ( C)
Got The specific surface area of the obtained PY-129 (C) is 79 m.
It was ² / g.

Reference Example 13 PY-129 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 5 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, filtration, washing with water to remove sodium chloride and polyethylene glycol, and vacuum drying in a hot air oven at 60 ° C. for 24 hours to obtain treated pigment PY-129 ( D)
Got The specific surface area of the obtained PY-129 (D) is 87 m.
It was ² / g.

Reference Example 14 PY-129 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 8 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, filtration, washing with water to remove sodium chloride and polyethylene glycol, and vacuum drying in a hot air oven at 60 ° C. for 24 hours to obtain treated pigment PY-129 ( E)
Got The specific surface area of the obtained PY-129 (E) is 105.
It was m ² / g.

E. Pigment Yellow PY-139 refinement by salt milling Reference Example 15 PY-139 (A) (specific surface area: 63 m ² / g) 250.0 g,
Sodium chloride 700g, rosin-modified maleic acid resin 107
g and 160 g of polyethylene glycol were charged and kneaded with a three-roll mill for 1 hour. Then add about 3 parts of this mixture.
Pour into warm water of L, stir for 1 hour with a high speed mixer while heating to 80 ° C. to make a slurry, then filter,
It was washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-139 (B). Obtained PY-13
The specific surface area of 9 (B) was 73 m ² / g.

Reference Example 16 PY-139 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 3 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, filtration, washing with water to remove sodium chloride and polyethylene glycol, and vacuum drying for 24 hours in a hot air oven at 60 ° C., treated pigment PY-139 ( C)
Got The specific surface area of the obtained PY-139 (C) is 80 m.
It was ² / g.

Reference Example 17 PY-139 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 5 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, filtration, washing with water to remove sodium chloride and polyethylene glycol, and vacuum drying for 24 hours in a hot air oven at 60 ° C., treated pigment PY-139 ( D)
Got The specific surface area of the obtained PY-139 (D) is 88 m.
It was ² / g.

Reference Example 18 PY-139 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 8 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high-speed mixer to form a slurry, filtration, washing with water to remove sodium chloride and polyethylene glycol, and vacuum drying for 24 hours in a hot air oven at 60 ° C., treated pigment PY-139 ( E)
Got The specific surface area of the obtained PY-139 (E) is 106.
It was m ² / g.

F. Pigment Yellow PY-110 refined by salt milling Reference Example 19 PY-110 (A) (specific surface area: 64 m ² / g) 250.0 g,
Sodium chloride 700g, rosin-modified maleic acid resin 107
g and 160 g of polyethylene glycol were charged and kneaded with a three-roll mill for 1 hour. Then add about 3 parts of this mixture.
Pour into warm water of L, stir for 1 hour with a high speed mixer while heating to 80 ° C. to make a slurry, then filter,
It was washed with water to remove sodium chloride and polyethylene glycol, and vacuum dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-110 (B). The obtained PY-11
The specific surface area of 0 (B) was 74 m ² / g.

Reference Example 20 PY-110 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded for 3 hours with a three-roll mill. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum-dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-110 ( C)
Got The specific surface area of the obtained PY-110 (C) is 79 m.
It was ² / g.

Reference Example 21 PY-110 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded with a three-roll mill for 5 hours. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum-dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-110 ( D)
Got The specific surface area of the obtained PY-110 (D) is 87 m.
It was ² / g.

Reference Example 22 PY-110 (A) (250.0 g), sodium chloride (700 g), rosin-modified maleic acid resin (107 g) and polyethylene glycol (160 g) were charged and kneaded for 8 hours with a three-roll mill. Next, this mixture is poured into about 3 L of warm water and heated to 80 ° C.
After heating for 1 hour with a high speed mixer to form a slurry, the mixture is filtered, washed with water to remove sodium chloride and polyethylene glycol, and vacuum-dried in a hot air oven at 60 ° C. for 24 hours to obtain a treated pigment PY-110 ( E)
Got The specific surface area of the obtained PY-110 (E) is 103.
It was m ² / g.

G. Formation and Evaluation of Green Colored Film Examples 1 to 5 PG-36 (specific surface area: 33 m ² / g) 56.0 g, PY-
138 (B) to (F) 24.0 g and γ-BL 920.0 g were charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours to give an 8% dispersion (GD1 to GD1).
5) was obtained.

To 112.5 g of the dispersion liquid (GD1 to 5), 67.5 g of the polyamic acid solution (PI-1) was added, 86.7 g of γ-BL, and M
A solution diluted with 33.3 g of MB was added and mixed to prepare a green coloring composition (GP1 to 5) having a pigment / polymer ratio of 47/53.

The green coloring composition (GP1 to 5) was applied onto a transparent substrate by a spinner so that the chromaticity y after film curing was y = 0.580, and then in air at 120 ° C. for 20 minutes in an oven. After drying, the film was cured in the air at 280 ° C. for 40 minutes in the air to form a green colored film.

Example 6 PG-36 (specific surface area: 56 m ² / g) 44.0 g, PY-
138 (B) 36.0 g and γ-BL 920.0 g were charged together with zirconia beads 1500 g, and a mill type disperser was used, and 420
The dispersion was carried out at 0 rpm for 3 hours to obtain an 8% dispersion liquid (GD6).

Pigment / polymer ratio as in Example 1:
A 47/53 green colored paste (GP6) was prepared to form a green colored film.

Examples 7 to 11 PG-36 (specific surface area: 33 m ² / g) 44.0 g, PY-
138 (B) to (F) 36.0 g and γ-BL 920.0 g were charged together with 1500 g of zirconia beads and dispersed using a mill type disperser at 4200 rpm for 3 hours to give an 8% dispersion (GD7-1).
1) was obtained.

Pigment / polymer ratio as in Example 1:
47/53 green coloring paste (GP7 to 11) was prepared to form a green coloring film.

Comparative Example 1 PG-36 (specific surface area: 33 m ² / g) 56.0 g, PY-
138 (A) 24.0 g and γ-BL 920.0 g were charged together with 1500 g of zirconia beads, and a mill type disperser was used.
The dispersion was carried out at 0 rpm for 3 hours to obtain an 8% dispersion liquid (GD12).

Pigment / polymer ratio as in Example 1:
Adjust the 47/53 green coloring paste (GP12),
A green colored film was formed.

Comparative Example 2 PG-36 (specific surface area: 33 m ² / g) 44.0 g, PY-
138 (A) 36.0 g and γ-BL 920.0 g were charged together with zirconia beads 1500 g, and a mill type disperser was used to
Dispersion was performed at 0 rpm for 3 hours to obtain an 8% dispersion liquid (GD13).
A green colored paste (GP13) 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 Examples 3 to 5 PG-36 (specific surface area: 33 m ² / g) 64.0 g, PY-
138 (A), (B), (D) 16.0 g and γ-BL 920.0 g were charged together with zirconia beads 1500 g and dispersed using a mill type disperser at 4200 rpm for 3 hours to give an 8% dispersion (GD1).
4-16) was obtained. A green coloring paste (GP14 to 1) 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.

As described above, the pastes (GP1 to 16) of Examples 1 to 11 and Comparative Examples 1 to 5 have a viscosity, a yield value, and a frozen temperature (-25).
Table 1 shows the rate of increase in viscosity after 3 months. Table 2 shows the chromaticity, film thickness, contrast and birefringence of the formed green colored film.

[0084]

[Table 1]

[0085]

[Table 2]

As the miniaturization of PY-138 progresses, P
When the content of Y-138 is 30% by weight, the specific surface area is 77 m.
^{When it was 2} / g or more, the contrast was 1000 or more, which was particularly good. Further, when the specific surface area is 77 m ² / g or more, the degree of improvement in contrast becomes small, and the specific surface area is 1
On the other hand, if it exceeds 20 m ² / g, the contrast will decrease,
The viscosity stability of the coloring composition also deteriorated. When the content of PY-138 was 40% by weight, the ratio of the yellow pigment increased and the contrast tended to decrease, but the effect of the specific surface area of the yellow pigment became more prominent. Specific surface area is 85m
^{When it was 2} / g or more, the contrast was 1000 or more, which was particularly good. When the specific surface area is 85 m ² / g or more, the degree of improvement in contrast becomes small, and the specific surface area is 1
On the other hand, if it exceeds 20 m ² / g, the contrast will decrease,
The viscosity stability of the coloring composition also deteriorated. When the content of PY-138 was 20% by weight, the yellowness of the green colored film was small, and the target chromaticity could not be achieved. Also, the effect of the specific surface area of the yellow pigment was small.

Further, comparing Example 1 and Example 6,
The smaller the specific surface area of PG-36, the higher the contrast.

Examples 12 to 15 PG-36 (specific surface area: 33 m ² / g) 52.0 g, PY-
28.0 g of 150 (B) to (E) and 920.0 g of γ-BL together with 1500 g of zirconia beads were charged and dispersed using a mill type disperser at 4200 rpm for 3 hours to give an 8% dispersion (GD17 ~).
20) was obtained.

Pigment / polymer ratio as in Example 1:
47/53 green coloring paste (GP17 to 20) was prepared to form a green coloring film.

Example 16 PG-36 (specific surface area: 56 m ² / g) 52.0 g, PY-
28.0 g of 150 (B) and 920.0 g of γ-BL were charged together with 1500 g of zirconia beads, and a mill type disperser was used to produce 420
Dispersion was performed at 0 rpm for 3 hours to obtain an 8% dispersion liquid (GD21).

Pigment / polymer ratio as in Example 1:
Adjust the green coloring paste (GP21) of 47/53,
A green colored film was formed.

Comparative Example 6 PG-36 (specific surface area: 33 m ² / g) 52.0 g, PY-
28.0 g of 150 (A) and 920.0 g of γ-BL were charged together with 1500 g of zirconia beads, and a mill type disperser was used.
The dispersion was carried out at 0 rpm for 3 hours to obtain an 8% dispersion liquid (GD22).
A green colored paste (GP22) having a pigment / polymer ratio of 47/53 was prepared in the same manner as in Example 1 to form a green colored film.

Table 3 shows the chromaticity and contrast of the green colored films formed from the pastes of Examples 12 to 16 and Comparative Example 6 (GP17 to 22).

[0094]

[Table 3]

As in the case of PY-138, the contrast of PY-150 was improved as the pigment was made finer, and the contrast was 1000 or more when the specific surface area was 84 m ² / g or more, which was particularly good. Further, when the specific surface area is 84 m ² / g or more, the degree of improvement in contrast becomes small.

Examples 17 to 20 PG-36 (specific surface area: 33 m ² / g) 44.0 g, PY-
138 (B)-(E) 28.0 g, PY-150 (B)-(E) 8.
0 g and γ-BL 920.0 g were charged together with 1500 g of zirconia beads, and the mixture was dispersed at 4200 rpm for 3 hours using a mill type disperser to obtain 8% dispersion liquids (GD23 to 26). Example 1
A green colored paste (GP23 to 26) having a pigment / polymer ratio of 47/53 was prepared in the same manner as in 1. to form a green colored film.

Examples 21 to 24 PG-36 (specific surface area: 33 m ² / g) 44.0 g, PY-
138 (B)-(E) 20.0g, PY-150 (B)-(E) 1
6.0 g and γ-BL 920.0 g were charged together with 1500 g of zirconia beads, and the mixture was dispersed at 4200 rpm for 3 hours using a mill type disperser to obtain an 8% dispersion liquid (GD27 to 30).

Pigment / polymer ratio as in Example 1:
47/53 green colored paste (GP27 to 30) was prepared to form a green colored film.

Example 25 PG-36 (specific surface area: 56 m ² / g) 44.0 g, PY-
138 (B) 20.0g, PY-150 (B) 16.0g and γ-B
L 920.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours.
% Dispersion (GD31) was obtained.

Pigment / polymer ratio as in Example 1:
Adjust the green coloring paste (GP31) of 47/53,
A green colored film was formed.

Comparative Example 7 PG-36 (specific surface area: 33 m ² / g) 44.0 g, PY-
138 (A) 28.0g, PY-150 (A) 8.0g and γ-B
L 920.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours.
% Dispersion (GD32) was obtained.

Pigment / polymer ratio as in Example 1:
Adjust the green coloring paste (GP32) of 47/53,
A green colored film was formed.

Comparative Example 8 PG-36 (specific surface area: 33 m ² / g) 44.0 g, PY-
138 (A) 20.0g, PY-150 (A) 16.0g and γ-B
L 920.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours.
% Dispersion (GD33) was obtained. Pigment / polymer ratio: 47/53 green colored paste (GP
33) was adjusted to form a green colored film.

As described above, the viscosities, yield values and frozen (-) of the pastes (GP23 to 33) of Examples 17 to 25 and Comparative Examples 7 and 8
Table 4 shows the rate of increase in viscosity at 25 ° C for 3 months. Table 5 shows the chromaticity, film thickness, contrast, and birefringence of the formed green colored film.

[0105]

[Table 4]

[0106]

[Table 5]

Even when PY-138 and PY-150 are used as the yellow pigment, the contrast is improved as the pigment is made finer, and the contrast is 1000 or more when the specific surface area is 80 m ² / g or more, which is particularly good. there were. Further, when the specific surface area is 80 m ² / g or more, the degree of improvement in contrast becomes small. Further, as compared with Examples 6 to 9, P
By adding Y-150, the film thickness at the same chromaticity can be reduced, and the viscosity stability of the coloring composition was also improved. However, when PY-150 was added to adjust the chromaticity, the content of PY-138 decreased, and the birefringence of the colored film increased.

Examples 26 to 29 PG-36 (specific surface area: 33 m ² / g) 48.0 g, PY-
138 (B)-(E) 28.0 g, PY-129 (B)-(E) 4.
0 g and 920.0 g of γ-BL were charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours to obtain 8% dispersion liquids (GD34 to 37). Example 1
In the same manner as above, a green coloring paste (GP34 to 37) having a pigment / polymer ratio of 47/53 was prepared to form a green coloring film.

Comparative Example 9 PG-36 (specific surface area: 33 m ² / g) 48.0 g, PY-
138 (A) 28.0g, PY-129 (A) 4.0g and γ-B
L 920.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours.
% Dispersion (GD38) was obtained. Pigment / polymer ratio: 47/53 green colored paste (GP
38) was adjusted to form a green colored film.

Table 6 shows the chromaticity and contrast of the green colored films formed from the pastes (GP34 to 38) of Examples 26 to 29 and Comparative Example 9 as described above.

[0111]

[Table 6]

Even when PY-138 and PY-129 are used as the yellow pigment, the contrast is improved as the pigment is made finer, and the contrast is 1000 or more when the specific surface area is 80 m ² / g or more, which is particularly good. there were. Further, when the specific surface area is 80 m ² / g or more, the degree of improvement in contrast becomes small.

Examples 30 to 33 PG-36 (specific surface area: 33 m ² / g) 52.0 g, PY-
138 (B)-(E) 26.4g, PY-139 (B)-(E) 1.6
g and γ-BL (920.0 g) were charged together with 1500 g of zirconia beads, and the mixture was dispersed at 4200 rpm for 3 hours using a mill type disperser to obtain an 8% dispersion liquid (GD39 to 42). Example 1
In the same manner as described above, a green coloring paste (GP39 to 42) having a pigment / polymer ratio of 47/53 was prepared to form a green coloring film.

Comparative Example 10 PG-36 (specific surface area: 33 m ² / g) 52.0 g, PY-
138 (A) 26.4g, PY-139 (A) 1.6g and γ-B
L 920.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours.
% Dispersion (GD43) was obtained. Pigment / polymer ratio: 47/53 green colored paste (GP
43) was adjusted to form a green colored film.

Table 7 shows the chromaticity and contrast of the green colored films formed from the pastes (GP39 to 43) of Examples 30 to 33 and Comparative Example 10.

[0116]

[Table 7]

Even when PY-138 and PY-139 are used as the yellow pigment, the contrast is improved as the pigment is made finer, and the contrast is 1000 or more when the specific surface area is 80 m ² / g or more, which is particularly good. there were. Further, when the specific surface area is 80 m ² / g or more, the degree of improvement in contrast becomes small.

Examples 34 to 37 PG-36 (specific surface area: 33 m ² / g) 52.0 g, PY-
138 (B)-(E) 26.4g, PY-110 (B)-(E) 1.
6 g and γ-BL 920.0 g were charged together with 1500 g of zirconia beads, and the mixture was dispersed at 4200 rpm for 3 hours using a mill type disperser to obtain an 8% dispersion liquid (GD44 to 47). Example 1
A green colored paste (GP44 to 47) having a pigment / polymer ratio of 47/53 was prepared in the same manner as in 1. to form a green colored film.

Comparative Example 11 PG-36 (specific surface area: 33 m ² / g) 52.0 g, PY-
138 (A) 26.4g, PY-110 (A) 1.6g and γ-B
L 920.0 g was charged together with 1500 g of zirconia beads, and dispersed using a mill type disperser at 4200 rpm for 3 hours.
% Dispersion (GD48) was obtained. Pigment / polymer ratio: 47/53 green colored paste (GP
48) was adjusted to form a green colored film.

Table 8 shows the chromaticity and contrast of the green colored films formed from the pastes of Examples 34 to 37 and Comparative Example 11 (GP44 to 48).

[0121]

[Table 8]

Even when PY-138 and PY-110 are used as the yellow pigment, the contrast is improved as the pigment is made finer, and the contrast is 1000 or more when the specific surface area is 80 m ² / g or more, which is particularly good. there were. Further, when the specific surface area is 80 m ² / g or more, the degree of improvement in contrast becomes small.

H. Preparation of Color Filter and Preparation of Liquid Crystal Display Example 38 Spin coating of the green coloring composition (GP2) on a non-alkali glass substrate (thickness 0.7 mm) on which a resin black matrix pattern having a thickness of 1.0 μm was formed. Then, it was heated and dried in air using an oven at 50 ° C. for 10 minutes, 90 ° C. for 10 minutes, and 110 ° C. for 20 minutes to obtain a polyimide precursor colored film having a film thickness of 1.5 μm. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Kogyo 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. Canon Inc. UV exposure machine PLA-5
01F was used to irradiate an ultraviolet ray having an intensity of 50 mJ / cm ² at a wavelength of 365 nm through a chrome photomask. After the exposure, the photoresist and the polyimide precursor colored film were simultaneously developed by immersing them in a developing solution composed of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. After edging, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate.
Further, the polyimide precursor colored film thus obtained was heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere to obtain a pattern of a green colored film having a thickness of 1.2 μm. Then, similarly, each of the blue coloring composition, the red coloring composition,
A pattern having a film 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 the mixture was 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 color filter is spin-coated with the obtained resin solution composition, and the mixture is heated at 100 ° C. for 5 minutes for 260 minutes.
An overcoat having a film thickness of 1.0 μm was formed by heating at 30 ° C. for 30 minutes. Next, when an ITO film was formed on the overcoat by a sputtering method, the film thickness was 14
IT of 00 angstrom and surface resistance of 15Ω / □
O was obtained. By the above operation, a color filter having three primary colors of red, green and blue, and having an overcoat and ITO was obtained.

Further, the color filter having the transparent electrode layer formed thereon is washed with a neutral detergent, and then an alignment film made of a polyimide resin is applied by a printing method, and a hot plate is used to remove the film.
Heated at 0 ° C. for 10 minutes. The film thickness was 0.07 μm. After this, rubbing the color filter substrate,
The sealing agent was applied by the dispensing method and heated on a hot plate at 90 ° C. for 10 minutes.

On the other hand, after similarly cleaning the substrate having the TFT array formed on the glass, the alignment film is applied and heated. Then, spherical spacers having a diameter of 5.5 μm were scattered, superposed on the color filter substrate, and heated at 160 ° C. for 90 minutes while applying pressure in an oven to cure the sealant. After the liquid crystal was injected 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 the liquid crystal display device.
The obtained liquid crystal display device had good color characteristics, and display characteristics with high contrast could be obtained. At this time, the contrast of the liquid crystal display device was 420.

Example 39 Example 35 except that the green coloring composition (GP9) was used.
The same operation was performed to complete the liquid crystal display device. The obtained liquid crystal display device had good color characteristics, and display characteristics with high contrast could be obtained. The contrast of the liquid crystal display device at this time was 410.

Example 40 Example 3 except that the green coloring composition (GP20) was used.
The same operation as in 5 was performed to complete the liquid crystal display device. The obtained liquid crystal display device had good color characteristics, and display characteristics with high contrast could be obtained. The contrast of the liquid crystal display device at this time was 410.

Example 41 Example 3 except that the green coloring composition (GP27) was used.
The same operation as in 5 was performed to complete the liquid crystal display device. The obtained liquid crystal display device had good color characteristics, and display characteristics with high contrast could be obtained. The contrast of the liquid crystal display device at this time was 410.

Comparative Example 12 Example 3 was repeated except that the green coloring composition (GP13) was used.
The same operation as in 5 was performed to complete the liquid crystal display device. The obtained liquid crystal display device had good color characteristics but low contrast. The contrast of the liquid crystal display device at this time was 280.

[0131]

Since the present invention is constructed as described above, a colored film having high contrast can be obtained by setting the specific surface area of the yellow pigment to 70 m ² / g or more. as a result,
A color filter with high contrast can be obtained, and a liquid crystal display device having good display characteristics can be obtained. Further, the effect of the specific surface area of the yellow pigment becomes remarkable when the content of the yellow pigment in all the pigment components is 30% by weight or more.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H048 BA02 BA45 BA47 BB02 BB42                       CA04 CA14                 2H091 FA02Y FA14Y FA41X FA41Z                       FC10 FC22 FC23 FC26 FC29                       GA01 GA03 GA06 GA08 GA09                       KA01 LA17                 4J038 DJ031 GA06 JB18 JB28                       JC38 KA06 KA08 MA07 MA10                       NA25 PB08

Claims (9)

[Claims] 1. A coloring composition for a color filter comprising at least a pigment, a polymer and a solvent,
The content of the yellow pigment in the pigment component is 30% by weight or more, and the specific surface area of the yellow pigment is 70 to 120 m ² / g.
And the yellow pigment comprises at least one quinophthalone pigment and one or more yellow pigments selected from the group consisting of isoindoline pigments, nickel azo complex pigments, and methine / azomethine pigments. A coloring composition for a color filter. 2. Pigment yellow PY-138 which is a quinophthalone pigment, Pigment Yellow PY-139 which is an isoindoline pigment, Pigment Yellow PY-150 which is a nickel azo complex pigment, and Pigment Yellow which is a methine / azomethine pigment. PY-129
The coloring composition for a color filter according to claim 1, which comprises one or more kinds of yellow pigments selected from the group consisting of: 3. A yellow pigment is pigment yellow PY-138.
And PY-150, The coloring composition for a color filter according to claim 1 or 2, wherein 4. The coloring composition for a color filter according to claim 3, wherein the amount ratio of Pigment Yellow PY-150 is in the range of 1 to 25% by weight based on the total pigment. 5. The coloring composition for a color filter according to claim 1, wherein the polymer is a resin having a carboxyl group. 6. The coloring composition for a color filter according to claim 5, wherein the polymer is a polyamic acid. 7. A color filter according to claim 1, wherein at least one color of the colored layer is a color filter having pixels each having a colored layer provided in a desired pattern for each color with an arbitrary number of colors. A color filter, which is a colored film formed by applying a coloring composition for a filter. 8. The green pixel among the pixels constituting the colored layer is
The chromaticity y in the C light source is 0.570 or more, and
When the chromaticity y is 0.580, the chromaticity x is 0.270 to 0.
The color filter according to claim 7, wherein the color filter has a value of 340 and a brightness Y value of 53 or more. 9. A liquid crystal display device using the color filter according to claim 7.