JP2000275423A - Color filter and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To restrain sublimation or decomposition of a colorant during manufacturing process and occurrence of wrinkling of a coloring film by an ITO sputtering, to improve yield during a color filter manufacture, and to provide a liquid crystal display device with high display quality, by setting a glass transition point of a resin higher than a specific temperature. SOLUTION: The glass transition point of a resin contained in a coloring film of a color filter is higher than 270 deg.C, preferably higher than 280 deg.C, more preferably higher than 290 deg.C. By setting the glass transition point of the resin higher than 270 deg.C, sublimation and/or decomposition of a colorant during a heat treatment process of the color filter is restrained, and occurrence of wrinkling on a coloring film during a process of an ITO sputtering can be prevented. The glass transition point of the resin is higher when it contains aromatic groups, and the glass transition point for acrylic resin is higher than that for polyimide or polyamide. Furthermore, polyimide is preferable in relation to workability of pixels and dispersion stability of coloring paste.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used for a liquid crystal display, an image pickup device and the like.

[0002]

2. Description of the Related Art As a color filter used for a liquid crystal display, an image pickup device, etc., a color filter formed using a polyimide and a pigment excellent in light resistance, heat resistance and chemical resistance is known (for example, Japanese Patent Laid-Open Publication No. Hei 11 (1995)). Showa 60-18
4202, JP-A-60-184203, JP-A-61-180203).

When making a color filter, usually,
A printing method or a photolithography method is used, but the photolithography method is currently mainstream in terms of pixel dimensional accuracy. Here, in order to prepare a color filter by a photolithography method using polyimide and a pigment, for example, JP-A-60-247603 and JP-A-61-7780.
As disclosed in Japanese Patent Application Publication No. 4 (1999) -104, a pattern processing technique using a positive photoresist is known. This pattern processing technology forms, for example, a green colored film with a colored paste composed of a polyamic acid and a pigment on a glass substrate,
A positive photoresist is applied on this to form a photoresist layer. Subsequently, the photoresist layer is exposed using an exposure apparatus. After the exposure, the development of the photoresist layer and the etching of the colored film of polyamic acid are simultaneously performed with the developer of the positive photoresist. Then, the photoresist layer which becomes unnecessary after the etching is peeled off, and the polyamic acid colored film is subjected to a heat treatment to complete the pattern processing of the green colored film. By repeating the above steps for the red and blue pixels and, if necessary, the black mask (black), a color filter is created.

In the above color filter manufacturing process, when the colored film is heat-treated at a temperature of 200 ° C. or more, the pigment contained in the colored film may be decomposed or sublimated.

[0005] Anthraquinone and / or diketopyrrolopyrrole red pigments such as color index numbers PR-177 and / or PR-2 are used as colorants.
In the case of a red pixel containing 54, a part of the red pigment sublimates in a heat treatment step at 200 ° C. or higher and adheres to the device. When the red pigment adheres to the apparatus by sublimation and accumulates, it causes dust and the like, and lowers the yield of the color filter.

[0006] Diazo yellow pigments such as color index numbers PY-17 and / or PY
In the case of a green pixel containing -83, a part of the yellow pigment is decomposed or sublimated in a heat treatment step at 200 ° C. or more, and the decomposed product or the sublimated product forms needle-like crystals on the pixel film surface and remains. It reduces the contrast of the color filter.

Further, when a metal oxide film such as ITO is sputtered, wrinkles are formed in the colored film, and the quality of the color filter is deteriorated.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and aims at sublimation or decomposition of a colorant in a manufacturing process.
An object of the present invention is to provide a liquid crystal display device that suppresses wrinkling of a colored film due to TO sputtering, improves the yield in the production of a color filter, and has a high display quality.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color filter comprising a transparent substrate provided with a patterned colored layer containing at least a resin and a colorant, wherein the resin has a glass transition point. Is 270 ° C. or higher, and a liquid crystal display device manufactured using the color filter.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The glass transition point of a resin in the present invention is measured by a differential scanning calorimeter method (DSC method), and an auxiliary line is drawn by a predetermined method on a DSC heating curve obtained by the measurement. The center temperature of the glass transition was determined.

In the present invention, the resin has a glass transition point of 270.
It has been found that by setting the temperature to not less than ° C, sublimation and / or decomposition of the colorant can be suppressed in the heat treatment step of the color filter, and further, wrinkles can be prevented from being generated in the colored film in the step of ITO sputtering. Therefore, the glass transition point of the resin contained in the colored film of the color filter is 270 ° C. or higher, preferably 280 ° C. or higher,
More preferably, the temperature is 290 ° C. or higher.

As the resin contained in the colored film of the color filter in the present invention, acrylic resin, alkyd resin, polyester, polyimide, polyurethane, polyamideimide, polyamide and the like can be used.

In general, the resin having an aromatic group has a higher glass transition point, and a polyimide or polyamide has a higher glass transition point than an acrylic resin. Further, polyimide is more preferably used than polyamide in view of the processability of the pixel and the dispersion stability of the colored paste.

The polyimide in the present invention is obtained by heating a polyamic acid having a structural unit represented by the following general formula (1), which is a precursor thereof, as a main component by heating or using an appropriate catalyst.
It is a polymer having an imide ring or another cyclic structure. 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.

[0016]

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

Preferred examples of R ¹ and R ² include a phenylene group, a naphthyl group, an anthryl group, a biphenylene group, a terphenylene group, a benzanilide group, a diphenylsulfone group and the like, and a phenylene group, a biphenylene group, a benzanilide group and a diphenylsulfone. Groups are more preferred.

[0019]

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Examples of the acid component containing R ¹ include, but are not limited to, the above-mentioned tetracarboxylic dianhydrides. Further, a tetracarboxylic dianhydride containing another cyclic hydrocarbon, an aromatic ring or an aromatic heterocycle can be copolymerized within a range where the glass transition point does not become 270 ° C. or lower. Examples of other acid dianhydrides are 3,3 ', 4,4
'-Benzophenonetetracarboxylic dianhydride, 3,3
', 4,4'-biphenyltrifluoropropanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -paraterphenyltetracarboxylic dianhydride, 3,3 ″,
4,4 ″ -methterphenyltetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2 1,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexenetetracarboxylic dianhydride, 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. However, the present invention is not limited to these.

[0021]

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Examples of the diamine component containing R ² include, but are not limited to, the diamines described above. Further, a diamine containing another cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring can be copolymerized within a range where the glass transition point does not become 270 ° C. or lower. Examples of other diamines include 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'-diaminodiphenyl ether, and the like. It is particularly preferable to include at least one selected from p-phenylenediamine, diaminobenzanilide and 3,3′-diaminodiphenylsulfone.

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. When siloxane diamine is copolymerized, 1 to 20 of all diamines
It is good to use mol% amount. 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. Two or more siloxane diamines may be used.

These polyamic acids can be synthesized by selectively combining tetracarboxylic dianhydride and diamine and reacting in a solvent. As a solvent for polyamic acid synthesis, an amide-based polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, or a lactone-based polar solvent may be used as a mixture. it can. Examples of the solvent other than the lactones include methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol and the like in addition to the amide-based polar solvent.

Lactones are aliphatic cyclic esters 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.

As the colorant contained in the color film of the color filter in the present invention, a pigment or a light-shielding agent can be used. As the pigment, those having high transparency and excellent light resistance, heat resistance and chemical resistance are preferable. Specific examples of typical pigments are indicated by color index (CI) numbers. Examples of yellow pigments include Pigment Yellow 13, 1
7, 20, 24, 83, 86, 93, 94, 95, 10
9, 110, 117, 125, 137, 138, 13
9, 147, 148, 153, 154, 166, 17
3, 185, etc., but are not limited thereto.
Examples of orange pigments include Pigment Orange 13,
31, 36, 38, 40, 42, 43, 51, 55, 5
9, 61, 64, 65, etc., but are not limited thereto. Pigment Red 9, 48, 97, 122, 123, 144, 149, 1
66, 168, 177, 180, 190, 192, 21
5, 216, 217, 220, 223, 224, 22
6, 227, 228, 240, 254, etc., but are not limited thereto. Examples of purple pigments include Pigment Violet 19, 23, 29, 32, 33, 3
6, 37, 38, 40, 50, etc., but are not limited thereto. Examples of blue pigments include Pigment Blue 15 (15: 1, 15: 2, 15: 3, 15: 4, 1
5: 6), 21, 22, 60, 64, etc., but are not limited thereto. Examples of green pigments include, but are not limited to, Pigment Green 7, 10, 36, 47, and the like. Examples of the black pigment include, but are not limited to, metal oxides such as carbon black, pigment black 7, and titanium black.
These pigments have been subjected to a surface treatment such as a rosin treatment, an acid group treatment, and a basic treatment as necessary.

The pigments are red, green,
Blue and three color pixels are combined and used in several colors to match the chromaticity characteristics of the CRT phosphor and the liquid crystal characteristics of the backlight and LCD.

Inorganic pigments and phthalocyanine pigments have high heat resistance, and pigments are not easily sublimated or decomposed in a heat treatment step. However, organic pigments such as red pigments and yellow pigments are not heat-treated at a temperature of 200 ° C. or more in the heat treatment step. Is easily sublimated or decomposed.

As the red organic pigment used for the red pixel, PR-177 of anthraquinone pigment or PR-254 of diketopyrrolopyrrole pigment is preferably used in view of the color characteristics of the color filter. When these pigments have a low glass transition point of the resin contained in the pixels, the pigments sublime in the heat treatment step and adhere to and accumulate on the device, causing dust and the like, which causes a reduction in the yield of the color filter. However, by using the resin having a glass transition point of 270 ° C. or higher of the present invention, sublimation of the pigment can be suppressed,
The yield of color filters can be increased.

As the yellow organic pigment used for the green pixel, diazo pigments PY-12, PY-17 and PY-83 are preferably used in view of the color characteristics of the color filter. When these pigments have a low glass transition point of the resin contained in the pixels, the pigments sublimate or decompose in the heat treatment step and adhere as needle-like crystals on the film surface of the pixels, lowering the contrast of the color filter. I will. However, by using the resin having a glass transition point of 270 ° C. or higher of the present invention, sublimation or decomposition of the pigment can be suppressed, and the contrast of the color filter can be increased.

In recent years, soluble pigment precursors such as those disclosed in JP-A-7-150068 and JP-A-7-188234 have been devised as colorants having both the advantages of both pigments and dyes. The soluble precursor pigment is a colorant having a property of being converted into a pigment after forming a coating film, although it is dissolved in the paste in the state of a colored paste as a dye.
Since pigment dispersion is unnecessary, there is an advantage that the color paste can be easily adjusted with good reproducibility. Furthermore, if the pigmentation is ideally advanced from the pigment precursor, the pigment will have a very fine particle size, so that a color filter with high contrast, high color purity and high transmittance can be obtained.

[0032]

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(R ₃ represents a methyl group or an ethyl group) For example, when a pigment precursor represented by the above general formula (2) is heat-treated to form a pigment, the diketopyrrolopyrrole-based pigment P
Converted to R-254.

If the pigmentation of the pigment precursor is carried out simultaneously with the thermosetting of the resin, it can be applied without changing the production process of the color filter. For example, when polyimide is used as the resin, the pigment precursor can be converted into the pigment simultaneously with the conversion of the polyamic acid into the polyimide by heat treatment, and a desired colored film can be obtained.

Here, when the glass transition point of the resin is low, the phenomenon that the pigment formed in the process of converting the pigment precursor into the pigment blows out on the film surface was observed. By using a resin having a temperature of 270 ° C. or higher, blowing of the formed pigment onto the film surface can be suppressed, and a desired colored film can be obtained.

In the colored paste used to form the colored layer of the color filter of the present invention, the resin and the colorant (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 resin is too small, the adhesion between the colored film and the substrate may be poor, and if the amount of the colorant is too small, the degree of coloring may become a problem. In the paste,
From the viewpoints of coatability, drying properties, etc., the solid content concentration of the resin and the colorant is 2 to 30%, preferably 3 to 25%,
More preferably, it is used in the range of 5 to 20%.

By mixing these colorants with a resin solution, a color paste is obtained. In this case, the colorant may be dispersed in the resin solution, or the colorant may be dispersed in a solvent in advance and then mixed with the resin solution. Regarding the selection of these production methods, it is preferable to select appropriate ones depending on the type of the coloring agent. The method for dispersing the colorant 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 and 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 by itself, ethanol, butanol, alcohols such as isopropanol, methyl cellosolve,
Organic solvents 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 laurylcarboxymethylhydroxyethylimidazolium 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 using an oven, a hot plate, and infrared rays at 50 to 180 ° C. for several seconds to several hours. 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 a temperature and increasing the temperature stepwise or while 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 is 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.

When a metal oxide film such as ITO is sputtered, if the resin contained in the pixel has a low glass transition point, wrinkles may be generated in the film.
By using a resin having a temperature of 70 ° C. or higher, generation of wrinkles can be suppressed, and a high-quality color filter can be obtained.

The liquid crystal display of the present invention is characterized by using the color filter of the present invention. By using the color filter of the present invention, it is possible to prevent a display defect from occurring in a liquid crystal display device and obtain a high quality display. Since the color filter of the present invention is used for a color liquid crystal display device, it is preferable to use a thin film transistor (TFT) for driving the liquid crystal display device of the present invention.

[0044]

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The measuring methods and tests in the examples are as follows. <Measurement of glass transition point> Differential scanning calorimetry (DSC method)
I went in. The equipment is DSC-2 type manufactured by Perkin-Elmer, and the data processing system TRC manufactured by Toray Research Center is used for data processing.
-THADAP-DSC-2 was used. Approximately 5 mg of the sample was packed in a standard aluminum container, which was pre-heat treated at 300 ° C.
The measurement was performed at a heating rate of 40 ° C./min. <Chromaticity> It was measured by MCPD2000 manufactured by Otsuka Electronics Co., Ltd. <Sublimation test> The heat-cured and cured colored film is placed on a hot plate set at a substrate temperature of 280 ° C., and a transparent glass substrate is placed on the colored film via a spacer of about 1 mm. It was left still. After 30 minutes, the transparent glass substrate was taken out, and the sublimate adhered to the substrate was visually observed. <Observation on film surface by microscope> Observation with a microscope is a microscope for inspection of large semiconductor and liquid crystal panels (Olympus BH3-M
JL) and automatic exposure microscope photography equipment (Olympus P
M-10AC) in reflection mode at a magnification of 500 times.

The raw materials and solvents of the polyamic acid in the examples are as follows.

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride OPDA: 4,4'-oxydiphthalic acid BTDA: 3,3', 4,4'-benzophenonetetracarboxylic dianhydride PMDA: pyromellitic dianhydride DAE: diaminodiphenyl ether PDA: phenylenediamine DABA: 4,4'-diaminobenzanilide SiDA: bis-3- (aminopropyl) tetramethylsiloxane DDS: 3,3'-diaminodiphenylsulfone MA : Maleic anhydride NMP: N-methyl-2-pyrrolidone γ-BL: γ-butyrolactone Synthesis of Polyamic Acid Solution Production Example 1 PDA 1 was added to a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot / cooling water, and a stirring device.
02.7 g (0.95 mol), 12.4 g (0.05 mol) of SiDA, 1408 g of γ-butyrolactone, N-methyl-2-pyrrolidone 3
Charged together with 52 g, ODPA 307.1 g (0.99 mol), γ-
289 g of butyrolactone, N-methyl-2-pyrrolidone
After adding 72 g, and reacting at 65 ° C. for 3 hours, adding 2.0 g (0.02 mol) of maleic anhydride and further reacting at 65 ° C. for 3 hours, a 20% polyamide having a viscosity of 32 poise (25 ° C.) An acid solution (PI-1) was obtained.

The polyamic acid solution PI-1 was spin-coated on a transparent substrate, dried in an air at 120 ° C. for 20 minutes using an oven, and then cured at 280 ° C. for 40 minutes in an air using an oven. Then, a polyimide film was formed.
The glass transition point of the obtained polyimide film was 306 ° C. Production Example 2 PDA 7 was added to a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot / cooling water, and a stirring device.
0.3 g (0.65 mol), DABA 68.2 g (0.65 mol), SiDA
12.4 g (0.05 mol) of 1521 g of γ-butyrolactone, N-
Charge with 380 g of methyl-2-pyrrolidone, ODPA
307.1 g (0.99 mol), γ-butyrolactone 311 g, N-
After adding 78 g of methyl-2-pyrrolidone and reacting at 65 ° C. for 3 hours, adding 2.0 g (0.02 mol) of maleic anhydride and further reacting at 65 ° C. for 3 hours, a viscosity of 56 poise (25 ° C. )), A 20% polyamic acid solution (PI-2) was obtained. The glass transition point was measured at 309 ° C. in the same manner as in Production Example 1. Production Example 3 DAE 1 was added to a reactor equipped with a thermometer, 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-butyrolactone, BTDA 161.0 g (0.50 mol), PMDA 106.8 g
(0.49 mol), reacted at 60 ° C. for 5 hours, and then added 1.96 g (0.02 mol) of maleic anhydride, and further added at 60 ° C.
After reacting for 1 hour, 1 with a viscosity of 15 poise (25 ° C.)
A 5% polyamic acid solution (PI-3) was obtained. When the glass transition point was measured in the same manner as in Production Example 1, it was 281 ° C. Production Example 4 DDS 1 was added to a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot / cooling water, and a stirring device.
17.8 g (0.475 mol), DABA 107.8 g (0.475 mol), Si
12.4 g (0.05 mol) of DA was 1036 g of γ-butyrolactone,
Charged with 1036 g of N-methyl-2-pyrrolidone, B
PDA 288.1 g (0.98 mol), γ-butyrolactone 258
g, N-methyl-2-pyrrolidone (258 g) was added.
After reacting at room temperature for 3 hours, 3.92 g of maleic anhydride (0.04m
ol) and further reacted at 80 ° C. for 3 hours, and then a 17% polyamic acid solution (P) having a viscosity of 20 poise (25 ° C.) was added.
I-4) was obtained. The glass transition point was measured at 296 ° C. in the same manner as in Production Example 1. Production Example 5 DAE 1 was added to a reaction vessel equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device using hot and cold water, and a stirring device.
90.0 g (0.95 mol), 12.4 g (0.05 mol) of SiDA, 1024 g of γ-butyrolactone, N-methyl-2-pyrrolidone 1
Charged with 024 g, BPDA 285.2 g (0.97 mol), γ-
Butyrolactone 256 g, N-methyl-2-pyrrolidone
After adding 256 g and reacting at 80 ° C. for 4 hours,
00 poise (25 ° C) 16% polyamic acid solution (PI
-5) was obtained. When the glass transition point was measured in the same manner as in Production Example 1, it was 254 ° C.

[0048]

[Table 1]

B. Heat resistance of red coloring film Example 1 60.8 g of PR-177, 19.2 g of PY-83 and 920.0 g of γ-butyrolactone were charged together with 1500 g of zirconia beads, and dispersed at 4200 rpm for 3 hours using a mill-type disperser, and 8% A dispersion (RD-1) was obtained.

To 112.5 g of the dispersion (RD-1) was added 67.5 g of the polyamic acid solution (PI-1) to γ-butyrolactone 8
A solution diluted with 6.7 g and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed, and a red colored paste (RP-
1) was obtained.

The red colored paste (RP-1) is spin-coated on a transparent substrate so that the chromaticity x after curing of the film becomes x = 0.580, and dried in the air at 120 ° C. for 20 minutes using an oven. After that, the film was cured in air using an oven at 280 ° C. for 40 minutes to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Example 2 A polyamic acid solution (P) was added to 112.5 g of the dispersion (RD-1).
I-2) A solution obtained by diluting 67.5 g with 86.7 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a red colored paste (RP-2).

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Example 3 A polyamic acid solution (P) was added to 112.5 g of the dispersion (RD-1).
I-3) A solution obtained by diluting 90.0 g with 64.2 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a red colored paste (RP-3).

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Comparative Example 1 A polyamic acid solution (P) was added to 112.5 g of the dispersion (RD-1).
I-5) A solution obtained by diluting 84.4 g with 69.8 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a red colored paste (RP-4).

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, considerable sublimate was observed.

When ITO was sputtered on the red colored film, wrinkles were found on the film. Example 4 30.4 g of PR-177, 49.6 g of PO-38 and 920.0 g of γ-butyrolactone were charged together with 1500 g of zirconia beads, and were dispersed for 3 hours at 4200 rpm using a mill-type disperser to obtain an 8% dispersion (RD-2). I got

To 112.5 g of the dispersion (RD-2) was added 67.5 g of the polyamic acid solution (PI-1) to γ-butyrolactone 8
A solution diluted with 6.7 g and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed, and a red colored paste (RP-
5) was obtained.

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Comparative Example 2 A polyamic acid solution (P) was added to 112.5 g of the dispersion (RD-2).
I-5) A solution obtained by diluting 84.4 g with 69.8 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a red colored paste (RP-6).

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, considerable sublimate was observed.

When ITO was sputtered on the red colored film, wrinkles were found on the film. Example 5 64.0 g of PR-254, 16.0 g of PY-83 and 920.0 g of γ-butyrolactone were charged together with 1500 g of zirconia beads, and were dispersed for 3 hours at 4200 rpm using a mill-type disperser to obtain an 8% dispersion (RD-3). I got

To 112.5 g of the dispersion (RD-3), 67.5 g of the polyamic acid solution (PI-2) was added to γ-butyrolactone 8
A solution diluted with 6.7 g and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed, and a red colored paste (RP-
7) was obtained.

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Example 6 A polyamic acid solution (P) was added to 112.5 g of the dispersion (RD-3).
I-3) A solution obtained by diluting 90.0 g with 64.2 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a red colored paste (RP-8).

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Comparative Example 3 A polyamic acid solution (P) was added to 112.5 g of the dispersion (RD-3).
I-5) A solution obtained by diluting 84.4 g with 69.8 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a red colored paste (RP-9).

The same operation as in Example 1 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, considerable sublimate was observed.

When ITO was sputtered on the red colored film, wrinkles were found on the film. Example 7 10.0 g of a soluble pigment precursor represented by the general formula (2) was dissolved in 50.0 g of cyclopentanone, and a polyamic acid solution (PI
-1) 50.0 g, γ-butyrolactone 94.4 g, and 3-methyl-3-methoxybutanol 45.6 g were added to obtain a red colored paste (RP-10).

A red colored paste (RP-10) is spin-coated on a transparent substrate so that the chromaticity x after curing of the film becomes x = 0.580, and dried in an air at 120 ° C. for 15 minutes using an oven. And then oven in 100 ℃ to 280 ℃
The temperature was raised in 30 minutes until the temperature reached 280 ° C., and then the temperature was maintained at 280 ° C. for 30 minutes, whereby the pigmentation of the soluble pigment precursor and the conversion of the polyamic acid to the polyimide were simultaneously performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Example 8 10.0 g of a soluble pigment precursor represented by the general formula (2) was dissolved in 50.0 g of cyclopentanone, and a polyamic acid solution (PI
-4) 58.8 g, 85.6 g of γ-butyrolactone and 45.6 g of 3-methyl-3-methoxybutanol were added to obtain a red colored paste (RP-11).

The same operation as in Example 7 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, almost no sublimate was found.

When ITO was sputtered on the red colored film, no wrinkles were found on the film. Comparative Example 4 10.0 g of a soluble pigment precursor represented by the general formula (2) was dissolved in 50.0 g of cyclopentanone, and a polyamic acid solution (PI
-4) 62.5 g, 81.9 g of γ-butyrolactone and 45.6 g of 3-methyl-3-methoxybutanol were added to obtain a red colored paste (RP-12).

The same operation as in Example 7 was performed to form a red colored film. When a sublimate test was performed on the obtained red colored film, considerable sublimate was observed.

When ITO was sputtered on the red colored film, wrinkles were found on the film. C. Heat resistance of green colored film Example 9 56.0 g of PG-36, 24.0 g of PY-17 and 920.0 g of γ-butyrolactone were charged together with 1500 g of zirconia beads, and dispersed at 4200 rpm for 3 hours using a mill-type dispersing machine.
An 8% dispersion (GD-1) was obtained.

To 112.5 g of the dispersion (GD-1), 67.5 g of the polyamic acid solution (PI-4) was added with γ-butyrolactone 8
A solution diluted with 6.7 g and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed, and a green colored paste (GP-
1) was obtained.

A green colored paste (GP-1) is spin-coated on a transparent substrate so that the chromaticity after film curing becomes y = 0.540, and dried in an air at 120 ° C. for 20 minutes using an oven. After that, the film was cured in air using an oven at 280 ° C. for 40 minutes to form a green colored film. The film surface of the obtained green colored film was observed under a microscope. Needle-like crystals considered to be decomposition products or sublimates of yellow pigment were not found on the film surface.

When ITO was sputtered on the green colored film, no wrinkles were found on the film. Example 10 A polyamic acid solution (P) was added to 112.5 g of the dispersion (GD-1).
I-3) A solution obtained by diluting 90.0 g with 64.2 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a green colored paste (GP-2).

The same operation as in Example 9 was performed to obtain a green colored film. The film surface of the obtained green colored film was observed under a microscope. Needle-like crystals considered to be decomposition products or sublimates of yellow pigment were not found on the film surface.

When ITO was sputtered on the green colored film, no wrinkles were found on the film. Comparative Example 5 A polyamic acid solution (P) was added to 112.5 g of the dispersion (GD-1).
I-5) A solution obtained by diluting 84.4 g with 69.8 g of γ-butyrolactone and 33.3 g of 3-methyl-3-methoxybutanol was added and mixed to obtain a green colored paste (GP-3).

The same operation as in Example 9 was performed to obtain a green colored film. The film surface of the obtained green colored film was observed under a microscope. Many needle-like crystals considered to be decomposition products or sublimates of yellow pigment were found on the film surface.

When ITO was sputtered on the green colored film, wrinkles were found on the film.

Table 2 summarizes the above results. In both the red pixel and the green pixel, if the glass transition point of the resin contained in the pixel is 270 ° C. or higher, sublimation of the pigment, ITO
Wrinkles on the film surface could be suppressed, but the glass transition point was 27
In the case of a resin having a temperature lower than 0 ° C., sublimation of the pigment and wrinkling of the film surface due to ITO occurred.

[0085]

[Table 2]

Example 11 A red coloring paste (RP-1) was spin-coated on a non-alkali glass substrate (0.7 mm thick) on which a resin black matrix pattern having a thickness of 1.0 μm was formed.
C. for 10 minutes, 90.degree. C. for 10 minutes, and 110.degree.
m was obtained. A positive photoresist (OFPR-800 manufactured by Tokyo Ohka Co., Ltd.) is applied on this film, and dried by heating at 80 ° C. for 20 minutes to obtain a film having a thickness of 1.1 μm.
Was obtained. Ultraviolet exposure machine P manufactured by Canon Inc.
Using LA-501F, 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 thin film were simultaneously developed by immersion in a developer consisting of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. After the etching, the unnecessary photoresist layer was stripped with methyl cellosolve acetate. Further, the thus obtained polyimide precursor colored thin film was heat-treated in a nitrogen atmosphere at 300 ° C. for 30 minutes to obtain a 1.6 μm-thick red colored thin film pattern.

Thereafter, similarly, a 1.6 μm-thick pattern was formed for each of the green paste and the blue paste.

After dissolving 65.05 g of trimellitic acid in 280 g of γ-butyrolactone, 74.95 g of γ-aminopropyltriethoxysilane was added.
Heat at 0 ° 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
g was 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 color filter, and heated at 100 ° C. for 5 minutes and at 260 ° C. for 30 minutes to form an overcoat having a thickness of 1.0 μm.

Next, when an ITO film was formed on the overcoat by a sputtering method, an ITO film having a thickness of 1400 Å and a surface resistance of 15 Ω / □ 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, after the color filter on which the transparent electrode layer has been formed is washed with a neutral detergent, an alignment film made of a polyimide resin is applied by a printing method, and is then heated on 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, superimposed on the color filter substrate, and heated at 160 ° C. for 90 minutes while applying pressure 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. Observation of the obtained liquid crystal display device revealed no display failure.

[0092]

According to the present invention, as described above, sublimation or decomposition of the colorant and wrinkles on the film surface due to ITO can be suppressed. As a result, the yield of color filters can be improved, and a liquid crystal display device with high display quality can be obtained.

Claims (13)

[Claims] 1. A color filter comprising a transparent substrate provided with a patterned colored layer containing at least a resin and a colorant, wherein the resin has a glass transition point of 270.
A color filter having a temperature of at least ℃. 2. The color filter according to claim 1, wherein the resin is polyimide. 3. The polyimide according to claim 1, wherein the residue of the acid component and / or the diamine component of the polyimide contains at least one selected from the group consisting of a phenylene group, a biphenylene group, a benzanilide group and a diphenylsulfone group. 2. The color filter according to 2. 4. A diamine component of a polyimide comprising p-phenylenediamine, diaminobenzanilide and 3,3'-
At least one selected from diaminodiphenyl sulfone
4. The color filter according to claim 3, comprising a kind. 5. The color filter according to claim 1, wherein the colorant contains at least one kind of organic pigment. 6. The color filter according to claim 5, wherein the colorant contains a red organic pigment of anthraquinone type and / or diketopyrrolopyrrole type. 7. A color index number PR for a colorant.
The color filter according to claim 6, comprising a red organic pigment of -177 and / or PR-254. 8. The color filter according to claim 5, wherein the colorant contains a diazo-based yellow organic pigment. 9. A color index number PY as a colorant.
The color filter according to claim 8, comprising a yellow organic pigment of -17 and / or PY-83. 10. The color filter according to claim 5, wherein the colorant is an organic pigment derived from a soluble pigment precursor. 11. The color filter according to claim 10, wherein the organic pigment is a diketopyrrolopyrrole-based pigment. 12. The color filter according to claim 11, wherein the organic pigment is an organic pigment having a color index number of PR-254. 13. A liquid crystal display device produced using the color filter according to claim 1. Description: