JPH1010539A - Resin composition for coating, liquid crystal oriented film in common use as protective film for lcd formed by using the same and production of liquid crystal oriented film in common use as protective film for lcd - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. for coating having a good adhesion property to glass substrates and color filters, coatability, transparency and orientability in addition to heat resistance and chemical resistance by using a specific polyimide resin. SOLUTION: The polyimide resin contg. diamine having sulfone and/or sulfide on the main chain at >=30mol% of the total molar number of the diamine and contg. aliphat. and/or alicyclic tetracarboxylic acid dianhydride at >=30mol% of the total molar number of the acid dianhydride is used. As a result, the resin compsn. has the good light transparency and orientability. Further, a high-concn. and low-viscosity soln. is prepd. by a heat treatment and half esterification of the tetracarboxylic acid dianhydride, by which the use of the compsn. as a resin for coating and a liquid crystal oriented film in common use as a protective film for LCD(liquid crystal display) having an excellent flattening function is made possible. Consequently, the differences in level of color filters, TFTs, common electrodes, etc., are eliminated and, therefore, flat substrates are obtd. The orientation defect which is heretofore resulted from the ruggedness of the substrates is eliminated and the domain and contrast ratio are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for coating, a film using the resin for coating, and a liquid crystal display (LCD) using the resin for coating.
The present invention relates to a protective film and a liquid crystal alignment film for use and a method for producing the same.

[0002]

2. Description of the Related Art Present color TFT (Thin Film Transistor)
In r) -LCD (Liquid Crystal Display), color filters are indispensable and are formed by dyeing, printing, electrodeposition, pigment dispersion, etc. To prevent elution into the liquid crystal,
A protective film is provided, an inorganic thin film made of ITO (Indiuum Tin Oxide) or the like is deposited thereon, and a thin liquid crystal alignment film having a liquid crystal alignment function is provided on the ITO.

The properties required for a color filter protective film include heat resistance, chemical resistance, adhesion to a glass substrate and a color filter, coating properties, transparency, and the like. Such coating materials having excellent heat resistance, chemical resistance and the like include acrylic resins described in JP-A-58-196506 and JP-A-62-119501 and JP-A-60-21.
A polyglycylyl methacrylate resin described in JP-A-6307 and a melamine resin described in JP-A-63-131103 have been proposed. Further, epoxy resins and polyimide resins have been proposed.

On the other hand, although the TFT substrate has an uneven structure of about 0.2 to 1 μm, a protective film having a flattening function is not particularly used, and a polyimide liquid crystal alignment film of about 70 nm is used. These steps cause a decrease in contrast ratio due to the generation of domains around the TFT and uneven brightness due to poor gaps, and solving these problems has become an urgent issue. In order to enable a larger screen, higher definition, and faster response in the future, it is necessary to flatten the uneven structure of the substrate and make the cell gap uniform.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to provide heat resistance, chemical resistance, adhesion to glass substrates and color filters, coating properties, and the like.
A novel coating composition that can satisfy the requirements of transparency, flatness, orientation, etc., a film using this composition, a protective film and liquid crystal alignment film for LCD with good flatness and orientation, and a method for producing the same. To provide.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies on the problems of the prior art, and as a result, have found that the use of a specific polyimide resin makes it possible to obtain a glass substrate and a color filter in addition to heat resistance and chemical resistance. Adhesion, coating properties,
The inventors have found that a coating resin composition exhibiting good properties of transparency, flatness, orientation, flatness and orientation can be obtained, and have completed the present invention.

That is, the present invention relates to one or more rigid diamine compounds selected from (a) a rigid diamine compound comprising (b) a rigid dihydrazide compound and (c) a diamine compound having sulfone and / or sulfide. A coating resin composition comprising an imide ring-containing organic polymer obtained by reacting a diamine component containing a compound with a tetracarboxylic dianhydride. And
The total amount of the compounds is preferably adjusted to be 30 mol% or more of the total number of moles of the diamine component.

The present invention further relates to a rigid diamine compound comprising (a) a rigid dihydrazide compound comprising (b) a component and (c) a diamine compound having a sulfone and / or sulfide. A coating resin composition containing an imide ring-containing organic polymer obtained by reacting a diamine component comprising a diamine compound other than these compounds with a diamine compound containing the same and a tetracarboxylic dianhydride. is there. This optional use includes (a) a rigid diamine compound comprising one part, (b) a rigid dihydrazide compound comprising one part, and (c) one or more compounds selected from diamine compounds having a sulfone and / or sulfide. Examples of the diamine compound other than the diamine compound include, for example, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 2,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,4′-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl)
Hexafluoropropane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis
(4-aminophenoxy) hexafluoropropane, 1,6-
Hexamethylenediamine, 1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,12-dodecamethylenediamine, azelaic dihydrazide, sebacic dihydrazide, 2,4'-diamino-3-methyl-stearylphenyl ether , 2,4'-diamino-3-methyl-laurylphenyl ether, 2,4'-diamino-3-methyl-palmitylphenylether, 2,4'-diamino-1-octyloxybenzene, 2,2-bis (4- (4-aminophenoxy) phenyl) octane, 2,2-bis (4- (4-aminophenoxy)
Phenyl) tridecane, 2,2-bis (4- (4-aminophenoxy) phenyl) pentadecane, bis (4- (4-aminobenzoyloxy) benzoic acid) octane, bis (4- (4-aminobenzoyloxy) benzoic acid ) Decane, bis (4- (4-aminobenzoyloxy) benzoic acid) dodecane, bis (4- (4-
Aminobenzoyloxy) benzoic acid) Methylcyclohexane, bis (4- (4-aminobenzoyloxy) benzoic acid)
Methane, bis (4- (4-aminobenzoyloxy) benzoic acid) butane, diaminosiloxane, 1,3-di (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, and the like, Two or more of these may be used in combination.

The above tetracarboxylic dianhydride includes:
Examples include aliphatic tetracarboxylic dianhydrides and / or alicyclic tetracarboxylic dianhydrides. Also,
In the above tetracarboxylic dianhydride, the total amount of the aliphatic tetracarboxylic dianhydride and / or the alicyclic tetracarboxylic dianhydride is preferably 30 mol% of the total number of moles of the tetracarboxylic dianhydride. Adjust so that it becomes the above.

Further, as the tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride and / or a mixture of an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride are also used. be able to. The imide ring-containing organic polymer preferably has a resin concentration of 15% by weight or more and an average molecular weight of 20,000 or less.

Further, the present invention uses the above-mentioned resin composition for coating, and has a film thickness of 0.5 to 2 μm and a light transmittance of 90% or more in a wavelength range of 400 to 800 nm. It is a film. . Further, the present invention provides a liquid crystal sandwiching substrate, on the surface of the substrate on which the electrodes are formed, after coating the coating composition, drying, dehydration and ring closure to form a polyimide layer, and then rubbing this LCD. This is a method of manufacturing a protective film for liquid crystal and a liquid crystal alignment film.

Further, the present invention is a protective film and liquid crystal alignment film for an LCD (Liquid Crystal Display) containing the coating composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for coating and the composition for a protective film and liquid crystal alignment film for LCD using the same according to the present invention comprise a diamine having a sulfone and / or sulfide on the main chain and a total number of moles of the diamine. 30 mol% or more of
Since it is a polyimide resin containing an aliphatic and / or alicyclic tetracarboxylic dianhydride in an amount of 30 mol% or more of the total number of moles of the acid dianhydride, it has good optical transparency and orientation.
Furthermore, since a high-concentration and low-viscosity solution is prepared by heat treatment and half-esterification of tetracarboxylic dianhydride, it is excellent in flattening function and can be used as a coating resin and a protective film for LCD and a liquid crystal alignment film. As a result, it is thought that there is no step in the color filter, TFT, common electrode, signal wiring electrode, scanning wiring electrode, etc., so that the substrate is flattened, and misalignment domains caused by unevenness of the substrate and the contrast ratio are improved. Can be Further, for the color filter substrate in the liquid crystal display device described in JP-A-6-16078, since a transparent electrode is not required, the properties of both a flattening film and a liquid crystal alignment film can be obtained by one-step coating. Therefore, its practicality is very high.

The diamine compound having a sulfone and / or sulfide used in the present invention includes 4,4'-
Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-
Diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, Bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3-aminophenoxy) phenyl) sulfide and the like may be used in combination of two or more, but good light transmittance In order to ensure the above, it is necessary that the ratio of the diamine having a sulfone and / or a sulfide is 30 mol% or more of the total number of moles of the diamine.

The rigid diamine and / or dihydrazide compound comprising a part used in the present invention includes p-phenylenediamine, m-phenylenediamine, and o-phenylenediamine.
Phenylenediamine, isophthalodil dihydrazide, terephthalodil dihydrazide, etc.
More than one kind may be used in combination, but in order to ensure a good liquid crystal alignment function, the rigid diamine and / or dihydrazide compound formed as a part of (1) should be used in an amount of 30 mol% or more of the total number of moles of the diamine. It is necessary to.

The flexible diamine and / or dihydrazide compound used as necessary includes 4,4'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-
Diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4 ' -Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone , Bis (4- (4-aminophenoxy) phenyl) sulfide, 2,
2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4-aminophenoxy) hexafluoropropane, 1,6-hexamethylenediamine, 1,12-dodecamethylenediamine, sebacic dihydrazide And sebacoil dihydrazide, and these may be used in combination of two or more.

As the diamine and / or dihydrazide compound other than the diamine having a sulfone and / or sulfide used as required, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether , 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 2,2-bis (4- (4-
Aminophenoxy) phenyl) propane, 2,2-bis (4-
Aminophenoxy) hexafluoropropane, 1,6-hexamethylenediamine, 1,12-dodecamethylenediamine,
Sebacic acid dihydrazide, sebacoil dihydrazide, p-
Phenylenediamine, m-phenylenediamine, o-phenylenediamine, isophthalodildihydrazide, terephthalodildihydrazide, and the like, and these may be used in combination of two or more, but in order to ensure a good liquid crystal alignment function p-phenylenediamine, m-phenylenediamine, o-
It is preferred to use a rigid diamine and / or dihydrazide compound consisting of one part such as phenylenediamine, isophthalodildihydrazide, terephthalodildihydrazide and the like.

Aliphatic tetracarboxylic dianhydride and / or
Or, as the alicyclic tetracarboxylic dianhydride, 1,2,
3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-Cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-biscyclohexanetetracarboxylic dianhydride, bicyclo (2,2,2) oct-7-ene-2,3,5, 6-tetracarboxylic dianhydride and the like, which may be used in combination of two or more, but in order to ensure good light transmission, the aliphatic tetracarboxylic dianhydride and / or It is necessary that the amount of the alicyclic tetracarboxylic dianhydride is 30 mol% or more of the total number of moles of the acid dianhydride.

The aromatic tetracarboxylic dianhydride optionally used is pyromellitic dianhydride, 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride, decamethylene trimellitate dianhydride, dimethylene trimellitate dianhydride, 3,3 ', 4,4'-tetracarboxyphenyl ether dianhydride And 2,2-bis (3,4-dicarboxylphenyl) hexafluoropropanoic dianhydride. These may be used in combination of two or more.

In the present invention, it is preferable that the ratio of the total number of moles of the diamine and / or dihydrazide to the number of moles of the acid dianhydride is in the range of 0.8 to 1.2, preferably 1.0. . The above aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride and tetracarboxylic dianhydride other than these tetracarboxylic dianhydrides and the above diamine and / or dihydrazide are dissolved in an inert solvent. To obtain a polyamic acid as a product. In this reaction, the reaction temperature was -30.
C. to 100.degree. C., and the reaction time is preferably 30 minutes to 48 hours. After the reaction is completed, the temperature is adjusted to 60 ° C to 25 ° C to adjust the molecular weight of the reaction product.
Heat treatment is performed at 0 ° C, preferably 120 ° C to 200 ° C, for 30 minutes to 72 hours. By the heat treatment after the reaction, the polyamic acid varnish has an average molecular weight of 20,000 or less and / or has a solid content of 15 or less.
Viscosity of 50 mPas or less at weight% or more, preferably 30 mPas
It is adjusted as follows. By this adjustment, good flatness as a protective film is imparted to the coating resin composition and the composition of the protective film for LCD and the liquid crystal alignment film using the same.

The inert solvent does not need to dissolve all of the above monomers, but is preferably one that dissolves the polyamic acid formed. Examples thereof include N-methyl-2-pyrrolidone and N, N-dimethylformamide. , N, N-dimethylacetamide, dimethylsulfoxide, 1,4-dioxane, γ
One or more of butyrolactone, γ-caprolactone and the like are used. In addition to these solvents, a solvent for improving the wettability to the glass substrate can be added before or after the reaction. Examples of these solvents include ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate,
Xylene, toluene, 1-ethoxy-2-acetoxypropane, diisobutyl ketone, methyl-n-hexyl ketone and the like are used.

The polyimide layer of the present invention is formed on a liquid crystal substrate by forming the above-described composition for a protective film and a liquid crystal alignment film for an LCD containing an inert solvent used during the reaction on a transparent electrode such as ITO in advance. After coating on the glass substrate
This is performed by dehydration and ring closure to form a polyimide layer. As a coating method, a spin coating method, a dipping method, a printing method, a spraying method, or the like is used. The dehydration ring closure temperature can be arbitrarily selected in the range of 100 to 400 ° C, preferably 150 to 250 ° C. The heating time is usually 1 minute to 6 hours, preferably 1 minute to 3 hours. In order to improve the adhesion between the glass and the polyimide resin, a coupling agent such as a silane coupling agent or a titanium coupling agent may be used between the polyimide resin and the polyimide resin.

The polyimide layer thus formed is used as a protective film for LCD and a liquid crystal alignment film by rubbing the surface. A liquid crystal display element can be obtained by a known method using a substrate having an LCD protective film and a liquid crystal alignment film.

[0024]

The present invention will be described below in more detail with reference to examples. However, the technical scope of the present invention is not limited to these examples.

[0025]

Example 1 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen introducing tube, 6.4893 g (0.03 mol) of 4,4'-diaminodiphenylsulfide was added to N-methyl-2-pyrrolidone 3
It was dissolved in 7.2997 g, 5.9440 g (0.03 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and the mixture was stirred and reacted at room temperature for 8 hours to prepare a polyamic acid varnish.
This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The obtained varnish has a viscosity of 33.3 mPa
The viscosity was 19.5 mPa · s (25 ° C.) at 22 ° C. and the weight average molecular weight in terms of standard polystyrene was 4,500.

The varnish having a total solid content of 22% by weight was spin-coated on a glass substrate at 1000 rpm, and was baked at 100 ° C. for 10 minutes and at 200 ° C.
Heat treatment was performed for 0 minutes to form a polyimide resin film having a thickness of 1.79 μm. As a result of measuring the light transmittance of this polyimide film with a spectrophotometer UL-3410 manufactured by Hitachi, Ltd., 96.
It showed good transmittance of 0% or more. This varnish was spin-coated on a glass substrate having a pattern of aluminum wiring height 1.48 μm and line spacing 15 μm (# 7059, a product name of Corning), and heat-treated at 100 ° C. for 10 minutes and 200 ° C. for 30 minutes. A polyimide resin film was formed. Approximately 20 nm of gold is vapor-deposited on the obtained polyimide layer, and an electron beam three-dimensional roughness analyzer: ERA-3000
(Product name of Elionix), the film thickness was 1.79.
The unevenness was 0.21 μm relative to μm, and the step was reduced.

This varnish was spin-coated at 1000 rpm on a glass substrate with ITO (# 7059, trade name of Corning) having a thickness of 3 cm × 4 cm × 1.1 mm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to obtain polyimide. A resin film was formed. Rubbing the surface of this polyimide film (roll indentation 0.4 mm, roll rotation speed 600 rpm, substrate moving speed 140 mm / min, rubbing frequency 1
Then, a liquid crystal sandwiching substrate was obtained as a liquid crystal alignment film. After rubbing, no peeling was observed on the coating film, indicating good adhesion. This liquid crystal sandwich substrate is assembled so that the upper and lower rubbing directions are almost parallel to each other, and the surroundings are epoxy-based thermosetting adhesive resin SE-4500 (Haven Chemical).
The product was sealed with Co. Ltd. (trade name) and heated and cured at 120 ° C. for 1 hour to form a liquid crystal cell. At this time, glass particles having a diameter of 5 μm were interposed as spacers in order to keep the gap of the liquid crystal cell constant. Liquid crystal ZLI-4792 (trade name, manufactured by Merck) was injected between the substrates by a vacuum impregnation method. Liquid crystal ZLI-4792 T
Heat treatment was performed at 130 ° C., which is higher than _NI , for 1 hour to form a liquid crystal display device. Then, two polarizing plates (Nitto Denko G12
In 20D), the panel is intersected and orthogonally closed to obtain normally closed characteristics. As a result, the liquid crystal display element did not suffer from poor alignment such as domains, and had a high display quality of 450: 1.

A color filter substrate was prepared by a known method, and the coating properties and adhesion on the substrate were examined. First, a color filter substrate was prepared by using a color filter pigment-dispersed photosensitive liquid PD-170 (trade name, manufactured by Hitachi Chemical Co., Ltd.) on # 7059 on which a black matrix was formed by chromium evaporation. Is 30μm × 100μm red,
A color filter in which pixels were arranged in stripes of three colors of green and blue was produced. In this embodiment, a pigment is used as the color-forming layer. However, a dye-type coloring material having a lower heat resistance and a more vivid color may be used.

Next, the varnish obtained by adding γ-aminopropyltriethoxysilane to the varnish in an amount of 2% by weight of the resin was spin-coated on the color filter substrate at 1000 rpm.
Heat treatment was performed at 10 ° C. for 10 minutes and at 250 ° C. for 30 minutes to form a color filter protective film. The thus prepared color filter with a coating film was observed in detail with an optical microscope. As a result, no voids, wrinkles or cracks were observed in the color filter or the protective film, and the surface was smooth and good.
The color filter substrate with the coating film is subjected to a pressure cooker test (121 ° C, 2 atm) for 24 hours,
A cross-cut test (JIS-K-5400) by tape peeling was performed to examine the adhesion to the color filter, but no peeling was observed.

[0030]

Example 2 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen introducing tube, 5.8258 g (0.03 mol) of isophthalodil dihydrazide was added to 31.5488 g of N-methyl-2-pyrrolidone.
5.9440 g (0.03 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was stirred and reacted at room temperature for 8 hours to prepare a polyamide acid varnish. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The obtained varnish had a viscosity of 37.9 mPa · s (25 ° C.) at 20% by weight and a weight average molecular weight in terms of standard polystyrene of 5,700.

This varnish was spin-coated on a glass substrate at 1000 rpm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 2.39 μm-thick polyimide resin film. The transmittance of this polyimide resin film was measured in the same manner as in Example 1, and as a result, good transmittance of 96.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern with a height of 1.69 μm of aluminum wiring and a line interval of 15 μm in the same manner as in Example 1.
The unevenness was 7 μm, and the step was reduced.

Further, as a result of fabricating a liquid crystal display element in the same manner as in Example 1, no defective alignment such as domains occurred, and the contrast was 800: 1, which was high display quality. No rubbing peeling was observed on this coating film, indicating good adhesion. Further, the results of evaluation of the coating property on the color filter and the results of the adhesion test were carried out in the same manner as in Example 1, but the coating property was good and no peeling was observed in the adhesion.

[0033]

Example 3 2.1625 g (0.005 mol) of bis (4- (3-aminophenoxy) phenyl) sulfone and 0.9710 of isophthalodyldihydrazide were placed in a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube. g (0.005 mol), 1.9814 g (0.01 mol) of 1,2,3,4-butanetetracarboxylic dianhydride
The polyamic acid varnish was prepared by dissolving in 20.460 g of methyl-2-pyrrolidone and stirring and reacting at room temperature for 8 hours. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour.
The obtained varnish was 20% by weight, the viscosity was 19.7 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 5,000.

The varnish was spin-coated on a glass substrate at 1000 rpm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.60 μm-thick polyimide resin film. The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 95.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern with a height of 1.00 μm of aluminum wiring and a line interval of 15 μm in the same manner as in Example 1.
The unevenness was 5 μm, and the step was reduced.

Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, no defective alignment such as a domain was generated, and the contrast was as high as 500: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0036]

Example 4 1.9419 g (0.01 mol) of isophthalodil dihydrazide, 4,4'-diaminodiphenylmethane was placed in a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube.
1.9827 g (0.01 mol), 3.9626 g (0.02 mol) of 1,2,3,4-butanetetracarboxylic dianhydride 31.54 of N-methyl-2-pyrrolidone
The polyamic acid varnish was prepared by dissolving in 88 g and reacting by stirring at room temperature for 8 hours. Add this polyamic acid varnish to 13
Heat treatment was performed at 0 ° C. for 1 hour. The obtained varnish is 20% by weight
And the viscosity was 20.4 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 5,000.

The varnish was spin-coated on a glass substrate at 1000 rpm and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.14 μm-thick polyimide resin film. The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 91.0% or more at 400 to 800 nm was shown.
This varnish was prepared in the same manner as in Example 1 to the height of the aluminum wiring.
As a result of evaluating the flatness on a glass substrate having a pattern of 1.00 μm and a line interval of 15 μm, a film thickness of 1.14 μm was compared with 0.21 μm.
And the step was reduced.

Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, no defective alignment such as domains occurred, and the contrast was high at 740: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0039]

Example 5 A four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube was charged with 2.9129 g (0.015 mol) of isophthalodil dihydrazide and 3.2447 g (0.015 ml) of 4,4'-diaminodiphenyl sulfide. 5.9439 g (0.03 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was added to N-methyl-2-pyrrolidone 4
The polyamic acid varnish was prepared by dissolving in 8.4060 g and stirring and reacting at room temperature for 8 hours. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The obtained varnish was 20% by weight, the viscosity was 10.9 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 3,100.

The varnish was spin-coated on a glass substrate at 800 rpm and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.14 μm-thick polyimide resin film. The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 95.0% or more at 400 to 800 nm was shown.
This varnish was prepared in the same manner as in Example 1 to the height of the aluminum wiring.
1.00μm, as a result of evaluating the flatness on a glass substrate having a pattern of 15μm line spacing, 0.10μm for a film thickness of 1.14μm
And the step was reduced. Furthermore, as a result of producing a liquid crystal display element in the same manner as in Example 1, no poor alignment such as domains occurred, and the contrast was 550: 1, which was high display quality. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0041]

EXAMPLE 6 2.1625 g (0.005 mol) of bis (4- (3-aminophenoxy) phenyl) sulfone and 0.9710 of isophthalodildihydrazide were placed in a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube. g (0.005 mol), 1.9814 g (0.01 mol) of 1,2,3,4-butanetetracarboxylic dianhydride
The polyamic acid varnish was prepared by dissolving in 20.460 g of methyl-2-pyrrolidone and stirring and reacting at room temperature for 8 hours. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour.
The obtained varnish was 20% by weight, the viscosity was 19.7 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 5,000.

This varnish was spin-coated on a glass substrate at 1000 rpm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.60 μm-thick polyimide resin film. The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 95.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern with a height of 1.00 μm of aluminum wiring and a line interval of 15 μm in the same manner as in Example 1.
The unevenness was 5 μm, and the step was reduced.

Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, no defective alignment such as a domain occurred, and the contrast was as high as 500: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0044]

Example 7 A four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube was charged with p-phenylenediamine 1.08.
10 g (0.01 mol), 4,4'-diaminodiphenyl sulfone 2.483
0g (0.01mol), 3,3 ', 4,4'-biscyclohexanetetracarboxylic dianhydride 4.2884g (0.014mol), decamethylene trimellitate dianhydride 3.1350g (0.006mol) were N-methyl -
The polyamic acid varnish was prepared by dissolving in 43.9496 g of 2-pyrrolidone and stirring and reacting at room temperature for 8 hours. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The obtained varnish had a viscosity of 78.6 mPa · s at 20 wt%, a viscosity of 32.7 mPa · s (25 ° C.) at 15 wt%, and a weight average molecular weight in terms of standard polystyrene of 15,000.

This 15% by weight varnish was applied to a glass substrate for 1000 r.
Spin coating was performed at pm, and heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a polyimide resin film having a thickness of 1.19 μm.
The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 90.0% or more at 400 to 800 nm was shown. This varnish was evaluated for flatness on a glass substrate having a pattern of aluminum wiring height 1.00 μm and line spacing 15 μm in the same manner as in Example 1.As a result, the varnish showed unevenness of 0.45 μm with respect to a film thickness of 1.19 μm. Was reduced.

Further, as a result of fabricating a liquid crystal display element in the same manner as in Example 1, no defective orientation such as domains occurred.
The contrast was high display quality of 500: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0047]

Example 8 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen introducing tube, 1.1652 g (0.006 mol) of isophthalodil dihydrazide and 3.0283 g (0.014 mol) of 4,4'-diaminodiphenyl sulfide were placed. , 3.9626 g (0.02 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was dissolved in 24.468 g of N-methyl-2-pyrrolidone and reacted by stirring at room temperature for 8 hours,
A polyamic acid varnish was prepared. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The resulting varnish is 25
The viscosity at 3% by weight is 39.5 mPas (25 ° C.), and the viscosity at 22% by weight is 25.4
mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 4,200.

The varnish was spin-coated on a glass substrate at 800 rpm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a polyimide resin film having a thickness of 2.40 μm. The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 96.0% or more at 400 to 800 nm was shown.
This varnish was prepared in the same manner as in Example 1 to the height of the aluminum wiring.
1.82μm, as a result of evaluating the flatness on a glass substrate having a pattern of line spacing 20μm, the film thickness 2.40μm to 0.58μm
And the step was reduced.

Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, no defective alignment such as domains occurred.
The contrast was a high display quality of 470: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0050]

Example 9 0.9710 g (0.005 mol) of isophthalodil dihydrazide, 2,2-bis (4- (4-aminophenoxy) were placed in a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube. Phenyl) hexafluoropropane 2.5923g (0.00
5mol), 1,2,3,4-butanetetracarboxylic dianhydride 1.981
4 g (0.01 mol) was dissolved in 22.179 g of N-methyl-2-pyrrolidone, and the mixture was stirred and reacted at room temperature for 8 hours to prepare a polyamic acid varnish. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The obtained varnish is 20% by weight and the viscosity is 15.
It was 8 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 4000.

The varnish was spin-coated on a glass substrate at 1000 rpm and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.67 μm-thick polyimide resin film. The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 95.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern with a height of 1.00 μm of aluminum wiring and a line interval of 15 μm in the same manner as in Example 1.
6 μm unevenness was exhibited, and the step was reduced.

Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, no defective alignment such as a domain occurred, and the contrast was as high as 500: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. Further, the coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1.
The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0053]

Example 10 A four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube was charged with 3.9626 g (0.02 mol) of 1,2,3,4-butanetetracarboxylic dianhydride and 1.8428 ethanol.
g (0.04 mol), 15.5770 g of N-methyl-2-pyrrolidone,
After reacting at 5 ° C for 1 hour, it was cooled to 20 ° C. 1.9419 g (0.01 mol) of isophthalodil dihydrazide, 4,4 ′
-Diaminodiphenyl sulfone (2.4831 g, 0.01 mol) was added, and the mixture was further stirred at room temperature for 4 hours to prepare a polyamic acid varnish. The obtained varnish is 35% by weight and the viscosity is 220mPas
(25 ° C.), the viscosity was 20.2 mPa · s (25 ° C.) at 20% by weight, and the weight average molecular weight in terms of standard polystyrene was 3,600.

This 20% by weight varnish was applied to a glass substrate for 1000 r.
Spin coating was performed at pm, and heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.07 μm-thick polyimide resin film.
The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 94.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern of aluminum wiring 0.90 μm in height and a line spacing of 15 μm in the same manner as in Example 1, and showed unevenness of 0.14 μm with respect to a film thickness of 1.07 μm. Was reduced.

Further, as a result of fabricating a liquid crystal display element in the same manner as in Example 1, no defective alignment such as domains occurred.
The contrast was high display quality of 420: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0056]

Example 11 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen introducing tube, 4.9662 g (0.02 mol) of 4,4'-diaminodiphenylsulfone and 3.8839 g (0.02 mol) of isophthalodildihydrazide were placed. , 7.9252 g (0.04 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was dissolved in 50.3259 g of N-methyl-2-pyrrolidone and reacted by stirring at room temperature for 8 hours to obtain a polyamide acid varnish. Prepared. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The resulting varnish was 35.7 mPas at 25% by weight (25 ° C.), and the viscosity was 18.5 mP at 21% by weight.
a · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 4,600.

This 21% by weight varnish was applied to a glass substrate at 800 rp.
m, and heat-treated at 100 ° C. for 10 minutes and 200 ° C. for 30 minutes to form a polyimide resin film having a thickness of 2.10 μm.
The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 96.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern with an aluminum wiring height of 1.48 μm and a line interval of 15 μm in the same manner as in Example 1.As a result, the varnish showed 0.12 μm unevenness for a film thickness of 2.10 μm, and showed a step. Was reduced.

Further, a liquid crystal display element was prepared in the same manner as in Example 1, and as a result, no defective orientation such as a domain was generated, and the contrast was as high as 500: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0059]

Example 12 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen introducing tube, 1.1652 g (0.006 mol) of isophthalodildihydrazide, 1,8-octamethylenediamine
2.0197 g (0.014 mol), N-methyl-2-pyrrolidone 28.
It was dissolved in 590 g, and 3.9626 g (0.02 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was stirred and reacted at room temperature for 8 hours to prepare a polyamic acid varnish. The obtained varnish was 20% by weight, the viscosity was 17.3 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 3,200.

The varnish was spin-coated on a glass substrate at 1000 rpm and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.69 μm-thick polyimide resin film. The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 95.0% or more at 400 to 800 nm was shown. This varnish was evaluated for flatness on a glass substrate having a pattern of aluminum wiring height 1.00 μm and a line interval 15 μm in the same manner as in Example 1, and as a result, a film thickness of 1.69 μm was 0.1.
The unevenness was 3 μm, and the step was reduced.

Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, no defective alignment such as domains occurred.
The contrast was high display quality of 390: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were conducted in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0062]

Example 13 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube, 4.9662 g (0.02 mol) of 4,4'-diaminodiphenylsulfone was added to N-methyl-2-pyrrolidone.
It was dissolved in 7864 g, and 3.9626 g (0.02 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was added thereto, and the mixture was stirred and reacted at room temperature for 8 hours to prepare a polyamic acid varnish. This polyamic acid varnish was heat-treated at 170 ° C. for 2 hours.
The obtained varnish has a viscosity of 32.0 mPas (25 ° C.) at 25% by weight 20
The viscosity in weight% was 13.7 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 4,600.

This 20% by weight varnish is applied to a glass substrate for 1000 r.
Spin coating was performed at pm, and heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.68 μm-thick polyimide resin film.
The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 96.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern of aluminum wiring 0.53 μm in height and a line spacing of 15 μm in the same manner as in Example 1, and as a result, showed a roughness of 0.12 μm with respect to a film thickness of 1.68 μm, showing a step. Was reduced.

Further, as a result of fabricating a liquid crystal display element in the same manner as in Example 1, no defective alignment such as domains occurred, and the contrast was 450: 1, which was a high display quality. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0065]

Example 14 A four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube was charged with 2.9720 g (0.015 mol) of 1,2,3,4-butanetetracarboxylic dianhydride and 1.382 of ethanol.
1 g (0.03 mol), N-methyl-2-pyrrolidone 10.9291 g was added,
After reacting at 85 ° C for 1 hour, it was cooled to 20 ° C. To this mixture was added 2.9129 g (0.015 mol) of isophthalodildihydrazide, and the mixture was further stirred at room temperature for 4 hours to prepare a polyamic acid varnish. The obtained varnish is 35% by weight and the viscosity is 125mPa
The viscosity was 11.4 mPa · s (25 ° C.) at s and 20% by weight, and the weight average molecular weight in terms of standard polystyrene was 4,400.

The varnish of 20% by weight was applied to a glass substrate for 1000 r.
Spin coating was performed at pm, and heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a polyimide resin film having a thickness of 1.14 μm.
The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 95.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern with an aluminum wiring height of 0.64 μm and a line interval of 15 μm in the same manner as in Example 1.As a result, unevenness of 0.21 μm was observed with respect to a film thickness of 1.14 μm. Was reduced.

Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, no defective alignment such as domains occurred.
The contrast was high display quality of 780: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were conducted in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0068]

Example 15 A four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube was charged with 3.9626 g (0.02 mol) of 1,2,3,4-butanetetracarboxylic dianhydride and 1.8428 ethanol.
g (0.04 mol), 14.648 g of N-methyl-2-pyrrolidone was added, and 85
After reacting at 20 ° C for 1 hour, the mixture was cooled to 20 ° C. 1.9419 g (0.01 mol) of isophthalodil dihydrazide, 4,4 ′
-Add 1.9827 g (0.01 mol) of diaminodiphenylmethane,
The mixture was further stirred at room temperature for 4 hours to prepare a polyamic acid varnish. The obtained varnish has a viscosity of 120 mPa
The viscosity in weight% was 10.3 mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 3,500.

The varnish of 20% by weight was applied to a glass substrate for 1000 r.
Spin coating was performed at pm, and heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.03 μm-thick polyimide resin film.
The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 90.0% or more at 400 to 800 nm was shown. This varnish was evaluated for flatness on a glass substrate having a pattern of aluminum wiring height 1.00 μm and a line interval 15 μm in the same manner as in Example 1, and as a result, irregularities of 0.20 μm were observed with respect to a film thickness of 1.05 μm, and a step was formed. Was reduced.

Further, as a result of producing a liquid crystal display device in the same manner as in Example 1, no defective alignment such as domains occurred.
The contrast was high display quality of 780: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were conducted in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0071]

Example 16 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube, 3.8839 g (0.02 mol) of isophthalodildihydrazide was added to 23.5395 of N-methyl-2-pyrrolidone.
g, and 3.9626 g (0.02 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was stirred and reacted at room temperature for 8 hours to prepare a polyamic acid varnish. This polyamic acid varnish was subjected to a heat treatment at 170 ° C. for 3 hours. The obtained varnish has a viscosity of 236 mPas at 25% by weight and a viscosity of 73 mPa at 20% by weight.
S (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 12,200.

The varnish having a total solid content of 20% by weight was spin-coated on a glass substrate at 1000 rpm, and was baked at 100.degree.
Heat treatment was performed for 0 minutes to form a polyimide resin film having a thickness of 1.84 μm. As a result of measuring the light transmittance of this polyimide film with a spectrophotometer UL-3410 manufactured by Hitachi, Ltd., 97.
It showed good transmittance of 0% or more. Example 1 using this varnish
In the same way as above, the height of aluminum wiring is 1.07μm, line spacing is 1
As a result of evaluating the flatness of a glass substrate having a pattern of 5 μm, unevenness of 0.46 μm was exhibited with respect to the film thickness of 1.84 μm, and the step was reduced.

Further, as a result of producing a liquid crystal display device in the same manner as in Example 1, no defective alignment such as domains occurred.
The contrast was a high display quality of 820: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. The coating property evaluation and the adhesion test on the color filter were conducted in the same manner as in Example 1. The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0074]

Example 17 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen introducing tube, 4.9662 g (0.02 mol) of 4,4′-diaminodiphenylsulfone and 3.8839 g (0.02 mol) of isophthalodildihydrazide were placed. 7.9252 g (0.04 mol) of 1,2,3,4-butanetetracarboxylic dianhydride was added to N-methyl-2-pyrrolidone 5
The polyamic acid varnish was prepared by dissolving in 0.3259 g, and stirring and reacting at room temperature for 8 hours. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The obtained varnish has a viscosity of 35.7 mPas at 25% by weight (25 ° C.) and a viscosity of 18.5 mPas at 21% by weight (2
5 ° C), and the standard polystyrene equivalent weight average molecular weight is 46.
00.

This 21% by weight varnish was applied to a glass substrate at 800 rp.
m, and heat-treated at 100 ° C. for 10 minutes and 200 ° C. for 30 minutes to form a polyimide resin film having a thickness of 2.10 μm.
The transmittance of this polyimide film was measured in the same manner as in Example 1, and as a result, good transmittance of 96.0% or more at 400 to 800 nm was shown. The varnish was evaluated for flatness on a glass substrate having a pattern with an aluminum wiring height of 1.48 μm and a line interval of 15 μm in the same manner as in Example 1. Was reduced.

Further, as a result of fabricating a liquid crystal display element in the same manner as in Example 1, no defective alignment such as a domain occurred, and the contrast was as high as 500: 1. No rubbing peeling was observed on this coating film, indicating good adhesion. Further, the coating property evaluation and the adhesion test on the color filter were performed in the same manner as in Example 1.
The coating property was smooth and good, and no peeling was observed in the adhesion test.

[0077]

Comparative Example 1 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube, and a nitrogen inlet tube, 1.0012 g (0.005 mol) of 4,4'-diaminodiphenyl ether was added with N.
-Methyl-2-pyrrolidone was dissolved in 8.3712 g, and pyromellitic dianhydride 1.0906 g was added thereto.
(0.005 mol), and the mixture was reacted by stirring at room temperature for 8 hours to prepare a 20% by weight polyamic acid varnish. This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The viscosity of the obtained varnish was 105 mPa · s (25
° C) and the weight average molecular weight in terms of standard polystyrene is 2
5000. This 20% by weight varnish was spin-coated on a glass substrate at 3000 rpm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 0.78 μm-thick polyimide film. As a result of measuring the light transmittance of this polyimide film with a spectrophotometer UL-3410 manufactured by Hitachi, Ltd., it showed a transmittance of 48.0% at 400 to 800 nm, and good light transmittance was not obtained.

The varnish was spin-coated at 1500 rpm on a glass substrate having a pattern with an aluminum wiring height of 1.00 μm and a line interval of 15 μm in the same manner as in Example 1, and the flatness was evaluated. Against
It showed irregularities of 0.72 μm, and good flatness was not obtained. Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, some domains were generated, and good orientation could not be obtained. The coating property on the color filter was evaluated in the same manner as in Example 1. However, yellowness became strong and good coating property was not obtained.

[0079]

Comparative Example 2 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen introduction tube, 2,2-bis (4- (4-
1.0012 g of aminophenoxy) phenyl) propane
(0.01 mol) in N-methyl-2-pyrrolidone 2
Dissolve in 9.310 g, and add 3,3 ', 4,4'
-Benzophenonetetracarboxylic dianhydride 3.222
3 g (0.01 mol) was added thereto, and the mixture was stirred and reacted at room temperature for 8 hours to prepare a 20% by weight polyamic acid varnish.
This polyamic acid varnish was heat-treated at 130 ° C. for 1 hour. The viscosity of the obtained varnish is 85 mPa · s (25
° C), and the weight average molecular weight in terms of standard polystyrene is 3
It was 1,000. The varnish having a total solid content of 20% by weight was spin-coated on a glass substrate at 800 rpm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a film having a thickness of 1.52
A μm polyimide film was formed. The light transmittance of this polyimide film was measured with a spectrophotometer UL-3410 manufactured by Hitachi, Ltd., and as a result, the transmittance was 70.degree.
0%, indicating that good light transmittance was not obtained.

This varnish was spin-coated at 800 rpm on a glass substrate having a pattern with an aluminum wiring height of 1.00 μm and a line interval of 15 μm in the same manner as in Example 1, and the flatness was evaluated. Against
The unevenness was 0.62 μm, and good flatness was not obtained. Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, some domains were generated, and good orientation could not be obtained. The coating property on the color filter was evaluated in the same manner as in Example 1. However, yellowness became strong and good coating property was not obtained.

[0081]

Comparative Example 3 In a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube, 1.9827 g (0.01 mol) of 4,4'-diaminodiphenylmethane was added with N-methyl-2-pyrrolidone. 700,3,3,3,4,4'-biphenyltetracarboxylic dianhydride 2.9422 g (0.01 mol) was added thereto,
The mixture was stirred and reacted at room temperature for 8 hours to prepare a 20% by weight polyamic acid varnish. 130 degreeC of this polyamic acid varnish
Heat treatment was performed for 1 hour. The resulting varnish has a viscosity of 62
mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 23,000. This 20% by weight varnish is spin-coated on a glass substrate at 1500 rpm,
Heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.45 μm-thick polyimide film. This polyimide film is coated with a spectrophotometer UL-3410 manufactured by Hitachi, Ltd.
As a result, the transmittance was 68.0% at 400 to 800 nm, and good light transmittance was not obtained.

This varnish was spin-coated at 1500 rpm on a glass substrate having a pattern with an aluminum wiring height of 1.00 μm and a line interval of 15 μm in the same manner as in Example 1, and the flatness was evaluated. Against
The unevenness was 0.60 μm, and good flatness was not obtained. Further, as a result of producing a liquid crystal display element in the same manner as in Example 1, some domains were generated, and good orientation could not be obtained. The coating property on the color filter was evaluated in the same manner as in Example 1. However, yellowness became strong and good coating property was not obtained.

[0083]

COMPARATIVE EXAMPLE 4 1.0814 g (0.01 mol) of p-phenylenediamine was placed in a four-necked flask equipped with a thermometer, a stirrer, a drying tube and a nitrogen inlet tube, and N-methyl-2-methyl-2-amine was added.
Dissolved in 22.0952 g of pyrrolidone,
4.4424 g (0.01 mol) of 4 '-(hexafluoroisopropylidene) diphthalic dianhydride was added,
The mixture was stirred and reacted at room temperature for 8 hours to prepare a 20% by weight polyamic acid varnish. This polyamic acid varnish is treated at 80 ° C. 8
Heat treatment was performed for a time. The viscosity of the obtained varnish is 120
mPa · s (25 ° C.), and the weight average molecular weight in terms of standard polystyrene was 35,000. This 20% by weight varnish is spin-coated on a glass substrate at 2000 rpm,
Heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a 1.50 μm thick polyimide film. This polyimide film is coated with a spectrophotometer UL-3410 manufactured by Hitachi, Ltd.
As a result, the transmittance was 91.0% or more at 400 to 800 nm, and the light transmittance was good.

This varnish was spin-coated at 2,000 rpm on a glass substrate having a pattern with an aluminum wiring height of 1.00 μm and a line interval of 15 μm in the same manner as in Example 1, and the flatness was evaluated. Against
The film showed irregularities of 0.75 μm, and good flatness was not obtained. Furthermore, a liquid crystal display device was prepared in the same manner as in Example 1, and as a result, the liquid crystal resistance was poor and good orientation could not be obtained. The coating property on the color filter was evaluated in the same manner as in Example 1. However, whitening was observed during the adhesion test, and good coating property was not obtained.

[0085]

Embodiment 18 A glass substrate # 7059 having a well-polished surface
(Thickness: 1.1 mm) According to a known example (Japanese Patent Laid-Open No. 6-160878, Japanese Patent Laid-Open No. 7-261181) on one of the substrates,
A matrix element consisting of an amorphous silicon-TFT and a wiring electrode to which a lateral electric field can be applied was formed.

At this time, the number of pixels is 40 (× 3) × 30, the pixel pitch is 80 μm in the horizontal direction (namely, between the common electrodes), 240 μm in the vertical direction (namely, between the scan electrodes), and the width of the scan electrode is 15 μm. The gap between the scanning electrodes was 68 μm. The height of the electrode is
It was 1.00 μm. 2 prepared in Example 1 above on a TFT substrate
A 2% by weight varnish to which γ-aminopropyltriethoxysilane was added at 2% by weight of the resin was spin-coated at 1000 rpm, and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to obtain a polyimide resin layer. At this time, 0.13μm for 1.79μm thickness
And the step was reduced.

On the other glass substrate, carbon fine particles (MO) manufactured by Cabot Corporation were used as a black matrix layer.
An epoxy resin mixed with 1% by weight of NARCH800 (particle size: 16 nm) was used, and PD-170 was used as a color filter coloring pigment. At this time, a color filter was prepared in which the width of the black matrix layer was 20 μm, the height was 0.52 μm, and one pixel was arranged in a stripe of 60 μm × 220 μm consisting of three colors of red, green and blue. Example 1
The 22% by weight varnish prepared in 2) was added with 2% by weight of γ-aminopropyltriethoxysilane for the resin, spin-coated at 800 rpm, and heat-treated at 100 ° C for 10 minutes and 200 ° C for 30 minutes to obtain a color filter. A protective film was formed. As a result, unevenness of 0.18 μm was shown with respect to the film thickness of 2.12 μm, and the step was reduced.

The surface of these polyimide films was subjected to a rubbing treatment (roll pressing amount: 0.4 mm, roll rotation speed: 600 rpm, substrate moving speed: 140 mm / min, rubbing frequency: once), and the liquid crystal sandwiching substrate was used as an LCD protective film and a liquid crystal alignment film. Obtained. After rubbing, no peeling was observed on the coating film, indicating good adhesion. The rubbing directions on the upper and lower interfaces were substantially parallel to each other, and the angle between the rubbing directions and the applied voltage direction was 85 degrees. This liquid crystal sandwiching substrate was combined, the periphery was sealed with an epoxy-based thermosetting adhesive resin SE-4500, and after heating and curing at 120 ° C. for 1 hour, a liquid crystal cell was produced. At this time, in order to keep the gap of the liquid crystal cell constant, polymer beads having a diameter of 4.0 μm were interposed as spacers. Liquid crystal MLC-2027 (trade name, manufactured by Merck) was injected between the substrates by a vacuum impregnation method. The liquid crystal MLC-2027 of T _NI
Heat treatment was performed at 100 ° C. for 1 hour at the above temperature to form a liquid crystal display element. After that, two polarizing plates (Nitto Denko's G1220
In D), the panel is interposed perpendicularly to obtain normally closed characteristics. When the characteristics were evaluated by modularization, the contrast ratio was sufficiently high at 100: 1, and nonuniformity of alignment, poor alignment such as reverse tilt domain, and display unevenness due to liquid crystal contamination did not occur at all. In addition, luminance unevenness due to gap failure was not visually recognized at all, and a display with high uniformity was obtained.

[0089]

Embodiment 19 A glass substrate # 7059 having a well polished surface
(Thickness: 1.1 mm) According to a known example (Japanese Patent Laid-Open No. 6-160878, Japanese Patent Laid-Open No. 7-261181) on one of the substrates,
A matrix element consisting of an amorphous silicon-TFT and a wiring electrode to which a lateral electric field can be applied was formed.

At this time, the number of pixels is 40 (× 3) × 30, the pixel pitch is 80 μm in the horizontal direction (namely, between the common electrodes), 240 μm in the vertical direction (namely, between the scan electrodes), and the width of the scan electrode is 15 μm. The gap between the scanning electrodes was 68 μm. The height of the electrode is
It was 1.0 μm. 20 prepared in Example 5 above on a TFT substrate
A varnish containing 2% by weight of γ-aminopropyltriethoxysilane added to a varnish by weight was spin-coated at 800 rpm and heat-treated at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to obtain a polyimide resin layer. At this time, 0.10μm for 1.14μm thickness
And the step was reduced.

On the other glass substrate, carbon fine particles (MO) manufactured by Cabot Corporation were used as a black matrix layer.
An epoxy resin mixed with 1% by weight of NARCH800 (particle size: 16 nm) was used, and PD-170 was used as a color filter coloring pigment. At this time, a color filter was prepared in which the width of the black matrix layer was 20 μm, the height was 0.52 μm, and one pixel was arranged in a stripe of 60 μm × 220 μm consisting of three colors of red, green and blue. The color filter was used in the fourth embodiment.
A varnish prepared by adding γ-aminopropyltriethoxysilane at 2% by weight to the 20% by weight varnish prepared in
Spin coating was performed at rpm, and heat treatment was performed at 100 ° C. for 10 minutes and at 200 ° C. for 30 minutes to form a color filter protective film. As a result, unevenness of 0.17 μm was exhibited with respect to the film thickness of 1.14 μm, and the step was reduced.

The surface of these polyimide films was subjected to a rubbing treatment (roll pressing amount: 0.4 mm, roll rotation speed: 600 rpm, substrate moving speed: 140 mm / min, rubbing frequency: once), and the liquid crystal sandwiching substrate was used as an LCD protective film and a liquid crystal alignment film. Obtained. After rubbing, no peeling was observed on the coating film, indicating good adhesion. The rubbing directions on the upper and lower interfaces were substantially parallel to each other, and the angle between the rubbing directions and the applied voltage direction was 85 degrees. This liquid crystal sandwiching substrate was combined, the periphery was sealed with an epoxy-based thermosetting adhesive resin SE-4500, and after heating and curing at 120 ° C. for 1 hour, a liquid crystal cell was produced. At this time, in order to keep the gap of the liquid crystal cell constant, polymer beads having a diameter of 4.0 μm were interposed as spacers. Liquid crystal MLC-2027 (trade name, manufactured by Merck) was injected between the substrates by a vacuum impregnation method. The liquid crystal MLC-2027 of T _NI
Heat treatment was performed at 100 ° C. for 1 hour at the above temperature to form a liquid crystal display element. After that, two polarizing plates (Nitto Denko's G1220
In D), the panel is interposed perpendicularly to obtain normally closed characteristics. When the characteristics were evaluated by modularization, the contrast ratio was sufficiently high at 100: 1, and nonuniformity of alignment, poor alignment such as reverse tilt domain, and display unevenness due to liquid crystal contamination did not occur at all. In addition, luminance unevenness due to gap failure was not visually recognized at all, and a display with high uniformity was obtained.

[0093]

Industrial Applicability The resin composition for coating, the resin for coating, the method for producing a protective film and liquid crystal alignment film for LCD using the same, the resin for coating and the protective film and liquid crystal alignment film for LCD using the same When a liquid crystal display element is manufactured by using the method described above, the substrate becomes flat because there are no steps such as color filters, TFTs, common electrodes, signal wiring electrodes, and scanning wiring electrodes. It is considered that the aperture ratio is improved. Compared with the conventional color filter protective film material, the thin film shows good flatness characteristics, so the loss of driving voltage of the liquid crystal can be suppressed, and the unevenness of the substrate is flattened to make the cell gap uniform. An effect on a large screen, high definition, high-speed response, and good liquid crystal orientation can be obtained by one-step coating, so that cost reduction can be achieved.

Continued on the front page (72) Inventor Yasuo Katsuya 4-1-1, Higashicho, Hitachi, Ibaraki Prefecture Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd. (72) Inventor Hisao Yokokura 7-1-1, Omikacho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd.Hitachi Research Laboratories (72) Katsumi Kondo Inventor 7-1-1, Omikacho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. Hitachi 1-1, Hitachi Ltd. (72) Inventor Hiroyuki Umeda 7-1-1, Omika-cho, Hitachi City, Ibaraki Pref. Hitachi Research Laboratory, Hitachi Ltd.

Claims (9)

[Claims] 1. A diamine containing one or more compounds selected from (a) a rigid diamine compound comprising one part, (b) a rigid dihydrazide compound comprising one part, and (c) a diamine compound having a sulfone and / or sulfide. A coating resin composition comprising an imide ring-containing organic polymer obtained by reacting a component with a tetracarboxylic dianhydride. 2. The total amount of one or more compounds selected from (a) a rigid diamine compound comprising one part, (b) a rigid dihydrazide compound comprising one part and (c) a diamine compound having a sulfone and / or sulfide. Is 30 mol% or more of the total number of moles of the diamine component. 3. The coating resin composition according to claim 1, wherein the tetracarboxylic dianhydride contains an aliphatic tetracarboxylic dianhydride and / or an alicyclic tetracarboxylic dianhydride. . 4. In the tetracarboxylic dianhydride, the total amount of the aliphatic tetracarboxylic dianhydride and / or the alicyclic tetracarboxylic dianhydride is 30 moles of the total number of moles of the tetracarboxylic dianhydride. % Or more. 5. The coating resin composition according to claim 1, wherein the imide ring-containing organic polymer has a resin concentration of 15% by weight or more and an average molecular weight of 20,000 or less. 6. One or more compounds selected from the group consisting of (a) a rigid diamine compound composed of one part, (b) a rigid dihydrazide compound composed of one part, and (c) a diamine compound having a sulfone and / or sulfide. A resin composition for coating comprising an imide ring-containing organic polymer obtained by reacting a diamine component comprising a diamine compound other than the above with a tetracarboxylic dianhydride. 7. A method using the resin composition for coating according to claim 1 wherein the film thickness is
Light transmittance of 9 in the range of 0.5 to 2 μm and wavelength of 400 to 800 nm
A film characterized by being at least 0%. 8. On a surface of the liquid crystal holding substrate on which the electrodes are formed,
8. A protective film and liquid crystal alignment for an LCD, comprising coating the composition for coating according to any one of claims 1 to 7, drying and dehydrating to form a polyimide layer, and then rubbing the polyimide layer. Manufacturing method of membrane. 9. An LCD (Liquid Crystal Displa) comprising the coating composition according to any one of claims 1 to 7.
y) Protective film for liquid crystal alignment film.