JPH09291150A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film excellent in transparency, heat resistance, chemical resistance, surface smoothness, tight adhesion, and sputtering resistance, and to provide a resin composition giving the cured film. SOLUTION: The composition comprises: a polyamic acid which is a product of the reaction of a tetracarboxylic dianhydride, a diamine, and an aminosilicon compound; an epoxy resin; an epoxy hardener; and a solvent. The amount of the epoxy resin is 50-250 pts.wt. per 100 pts.wt. the polyamic acid, while that of the epoxy hardener is 1-80 pts.wt. per 100 pts.wt. the epoxy resin.

Description

Detailed Description of the Invention

[0010]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition and a cured film obtained by heating and curing the composition, and the cured film includes a color filter, a protective film for an LED light emitting body, and a TFT. And a transparent insulating film formed between the transparent electrodes and between the transparent electrode and the alignment film.

[0011]

2. Description of the Related Art During the manufacturing process of liquid crystal display elements and the like, various chemical treatments such as organic solvents, acids and alkaline solutions are carried out, and when forming wiring electrodes by sputtering, the surface is locally exposed. May be heated to high temperatures. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements.

These protective films are required to have various characteristics capable of withstanding the above-mentioned treatments. In particular,
Chemical resistance such as solvent resistance, acid resistance, alkali resistance, water resistance, heat resistance, adhesion to the underlying substrate such as glass,
Transparency, scratch resistance, coatability, flatness, light resistance, etc. are required so as not to deteriorate such as coloring over a long period of time. Especially, when used as a color filter protective film, importance is attached to flatness. STN (Super-Twisted-Nem
atic) color filter protective film is 0.05μ
Flatness of m or less, and for TFT (Thin Film Transistor), flatness of 0.1 to 0.2 μm is required.

Examples of the protective film material excellent in these characteristics include (meth) acrylic resin compositions described in JP-A-5-78453 and JP-A-5-255460, and JP-A-4-170421. And JP-A-5-140
Epoxy resin composition described in JP-A No. 274, JP-A-63
The silica-based resin composition described in JP-A-218771 and the polyimide-based resin composition described in JP-A-1-229203 have been studied. However, each of these conventionally proposed materials has drawbacks, and there is no well-balanced material that satisfies all the required characteristics.

For example, a (meth) acrylic resin is generally excellent in transparency, but has a drawback that the flattening function is not sufficient. In addition, since the heat resistance is insufficient, there is a problem that wrinkles and cracks are generated on the coating film surface during sputtering of indium tin oxide (ITO) or the like. In addition, there is a problem in the adhesion to ITO and the patterning property.

Epoxy resins have good adhesion but insufficient heat resistance. In addition, there is a problem in the flattening function. Further, although the silica-based resin has good transparency and heat resistance, it has a problem that it does not have a sufficient flattening function and cracks occur during sputtering of ITO or the like.
Moreover, high temperature heating is required when the film is cured. On the other hand, the polyimide resin has good heat resistance, but has a problem that the planarization function is not sufficient and the transparency is essentially inferior.
Moreover, high temperature heating is required when the film is cured.

[0016]

The object of the present invention is to solve the problems of the above resins, and to improve transparency, heat resistance,
It is an object of the present invention to provide a cured film which is well balanced in chemical resistance, flatness, adhesion and spatter resistance, and a resin composition for obtaining this cured film.

[0017]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventors have found that a polycarboxylic acid obtained from a reaction of a tetracarboxylic dianhydride, a diamine, an aminosilicon compound, an epoxy resin, Further, they have found that a cured film obtained by heating and curing a resin composition composed of an epoxy curing agent and a solvent can achieve the above object, and completed the present invention.

The present invention has the following configuration. (1) A resin composition comprising a polyamic acid (hereinafter, abbreviated as silicon-containing polyamic acid) composed of a reaction product of tetracarboxylic dianhydride, a diamine and an aminosilicon compound, an epoxy resin, an epoxy curing agent and a solvent. Epoxy resin is 50 to 250 parts by weight with respect to 100 parts by weight of silicon-containing polyamic acid, and
1 part of epoxy curing agent to 100 parts by weight of epoxy resin
A thermosetting resin composition, wherein the thermosetting resin composition is about 80 parts by weight. (2) The silicon-containing polyamic acid is obtained by converting X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of aminosilicon compound into the following formulas (101) and (10).
The thermosetting resin composition according to item (1), which is obtained by reacting at a ratio such that the relationship of 2) is established. 1.8 ≦ Z / (X−Y) ≦ 2 (101) Y / Z ≦ 0.4 (102) (3) Heat the thermosetting resin composition according to item (1). ,
A cured film obtained by curing. (4) A color filter using the cured film according to item (3) as a protective film. (5) A liquid crystal display device using the color filter having the cured film according to the item (3) as a protective film. (6) A solid-state imaging device using the color filter having the cured film according to item (3) as a protective film. (7) A liquid crystal display device using the cured film according to item (3) as a transparent insulating film formed between a TFT and a transparent electrode. (8) A liquid crystal display device using the cured film according to item (3) as a transparent insulating film formed between a transparent electrode and an alignment film. (9) An LED light-emitting body, which uses the cured film according to item (3) as a protective film.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Specific examples of the tetracarboxylic acid dianhydride used in the present invention include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2 ′,
3,3′-benzophenone tetracarboxylic dianhydride,
2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylsulfone tetra Carboxylic dianhydride, 2,3
3 ', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic acid dianhydride , 2, 3, 3 ',
4'-diphenyl ether tetracarboxylic dianhydride,
2,2- [Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-
100, manufactured by Shin Nippon Rika Co., Ltd., and the like. Among these, it gives a resin with good transparency 3,
3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl )] Hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, Shin Nippon Rika Co., Ltd.)
Manufactured), and 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid dianhydride is particularly preferable.

Specific examples of the diamine include 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone and bis [4- (4-aminophenoxy) phenyl] sulfone. , Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl ] Sulfone, [4- (3-aminophenoxy) phenyl]
[3- (4-aminophenoxy) phenyl] sulfone,
2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like can be mentioned. Among these, it gives a resin with good transparency 3,
3'-diaminodiphenyl sulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are preferable,
3,3'-diaminodiphenyl sulfone is particularly preferred.

Specific examples of the aminosilicon compound include:
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4 -Aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p
-Aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, m-aminophenylmethyldiethoxysilane and the like can be mentioned. Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane are preferable, and 3-aminopropyltriethoxysilane is particularly preferable.

Specific examples of the solvent used in the polymerization reaction for obtaining the silicon-containing polyamic acid include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, and other diethylene glycols, ethylene glycol. Mention may be made of ethylene glycols such as monoethyl ether acetate and ethylene glycol monoisopropyl ether, and ethyl lactate and cyclohexanone.

The above solvents can be used alone or as a mixed solvent of two or more kinds, and when the above solvent is contained in an amount of 70 parts by weight or more based on 100 parts by weight of the total solvent, as a mixed solvent with a solvent other than the above solvents. Can also be used.

The reaction method of the silicon-containing polyamic acid is as follows:
X mole of tetracarboxylic dianhydride, Y mole of diamine, and Z mole of aminosilicon compound are reacted in the above solvent. At this time, X, Y and Z are expressed by the following formula (10
It is determined so that the relationship of 1) and Expression (102) is established.
Outside of this range, the flatness, transparency and adhesion of the cured film to the substrate may be reduced. 1.8 ≦ Z / (X−Y) ≦ 2 (101) Y / Z ≦ 0.4 (102) The reaction solvent is 100 parts by weight of the total amount of the reaction solvent and the starting material.
It is recommended to use 60 parts by weight or more. If it is less than this range, the solubility of the raw material is remarkably deteriorated and the selection range of the solvent is narrowed, which is not preferable. The reaction is carried out at 0 to 40 ° C. for 0.2 to 20
It is good to react for a time. The order of addition of the reaction raw materials to the reaction system is that tetracarboxylic acid dianhydride, diamine and aminosilicon compound are simultaneously added to the reaction solvent, and diamine and aminosilicon compound are dissolved in the reaction solvent, and then tetracarboxylic acid dianhydride is added. It is possible to use any method such as adding a substance, or reacting a tetracarboxylic acid dianhydride with a diamine in advance, and then adding an aminosilicon compound to the reaction product.

The epoxy resin is not particularly limited as long as it is compatible with other components forming the thermosetting resin composition of the present invention, but is preferably a bisphenol A type epoxy resin or a glycidyl ester type epoxy resin. And alicyclic epoxy resins. Of these, alicyclic epoxy resins, which are excellent in transparency, are more preferably used.

Specific examples of the epoxy resin include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, and Epicoat 190.
P, Epicoat 191P (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite CY177, Araldite CY184 (trade name, Nippon Ciba Geigy Co., Ltd.)
Manufactured by Daicel Chemical Industry Co., Ltd.).

As the epoxy curing agent, there are acid anhydride type curing agents, polyamine type curing agents, polyphenol type curing agents, catalyst type curing agents and the like, but acid anhydride type curing agents are preferable from the viewpoint of coloring and heat resistance. .

Specific examples of acid anhydride type curing agents include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, and anhydrous. Examples thereof include aromatic polycarboxylic acid anhydrides such as trimellitic acid. Among these, trimellitic anhydride is particularly preferable from the viewpoint of the balance between heat resistance and solubility in a solvent.

The thermosetting resin composition of the present invention contains 50 to 250 parts by weight of an epoxy resin with respect to 100 parts by weight of a silicon-containing polyamic acid, and 1 to 80 parts of an epoxy curing agent with respect to 100 parts by weight of an epoxy resin. Parts by weight. If the amount of the epoxy resin is less than 50 parts by weight, sufficient flatness cannot be obtained, and if it exceeds 250 parts by weight, heat resistance and chemical resistance may be impaired. The ratio of the epoxy resin and the epoxy curing agent is 0.5 to 1.2 for the epoxy group and the carboxylic acid anhydride group or the carboxylic acid group as the epoxy curing agent.
It is preferable to add it in a double equivalent amount. As the solvent used in the resin composition of the present invention, the solvent used in the polymerization reaction when synthesizing the silicon-containing polyamic acid can be used as it is. The solid content of the thermosetting resin composition will be selected according to the film thickness of the coating film, but it is generally contained in the range of 30 to 50 parts by weight in 100 parts by weight of the resin composition. .

The thermosetting resin composition according to the present invention may contain components other than the above components, if necessary, within a range not impairing the object of the present invention. Examples of such other components include coupling agents and surfactants.

The coupling agent is used to improve the adhesion to the substrate, and the solid content of the thermosetting resin composition is 100 parts by weight (the remainder of the resin composition excluding the solvent). 10 parts by weight or less is used. As the coupling agent, silane-based, aluminum-based and titanate-based compounds are used.

Specifically, silanes such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltrimethoxysilane, acetoalkoxyaluminum diisopropylate, etc. And aluminum titanate such as tetraisopropyl bis (dioctyl phosphite) titanate.

The surface active agent is used for improving the wettability, leveling property and coating property to the base substrate, and is 0.0 to 100 parts by weight of the thermosetting resin composition.
It is used by adding 1 to 1 part by weight. As the surfactant, a silicon-based surfactant, an acrylic-based surfactant or the like is used. Specifically, Byk-300, Byk-
306, Byk-335, Byk-310, Byk-3
41, Byk-344, Byk-370 (these product names,
Silicon-based products such as BYK-Chemie, Byk-
Acrylics such as 354, ByK-358, Byk-361 (these product names, manufactured by BYK-Chemie Co., Ltd.) can be mentioned.

A coating film can be formed by applying the thermosetting resin composition prepared as described above to the surface of a substrate and removing the solvent by heating. For coating the thermosetting resin composition on the surface of the substrate, a coating film can be formed by a conventionally known method such as a spin coating method, a roll coating method or a dipping method. Next, this coating film is heated (prebaked) with a hot plate, an oven, or the like.
The heating conditions vary depending on the type and mixing ratio of each component,
It is usually 70 to 110 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate. Then, to cure the coating film, 180 to 250 ° C., preferably 200 to 250 ° C.
After heating from 250 ° C, more preferably 150 ° C, 2
A cured film can be obtained by heating at 00 to 250 ° C. for 30 to 90 minutes in an oven and 5 to 30 minutes in a hot plate. The cured film thus obtained is heated to: 1) a polyamic acid dehydrates and cyclizes to form an imide bond; and 2) an alkoxysilyl group, which is a hydrolyzing group at a molecular end, is hydrolyzed and condensed to give a high molecular weight. 3) Epoxy resin is hardened and becomes high molecular weight, so it is very tough and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion and spatter resistance, and is useful as a protective film for color filters. .

In addition, the cured film has excellent characteristics as an optical material such as transparency, so that the LED light emitting element,
Protective film for various optical materials such as light receiving element, and TFT
It can also be used as a transparent insulating film between the transparent electrode and the transparent electrode, or between the transparent electrode and the alignment film.

The above cured film is a protective film for a color filter,
As a liquid crystal compound and composition for producing a liquid crystal display element used as a transparent insulating film between a TFT and a transparent electrode and a transparent insulating film between a transparent electrode and an alignment film, a liquid crystal manufactured by Chisso Corporation is particularly preferable, It is not limited to these. More specifically as the liquid crystal compound, the following general formulas (1) to
The compound represented by (8) is preferable.

[0037]

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In the formulas (1) to (3), R1 represents an alkyl group having 1 to 10 carbon atoms, Y1 represents a fluorine atom, a chlorine atom, OCF3, OCF2H, CF3, CF2H or CFH2, L1, L2, L3 and L4 each independently represent a hydrogen atom or a fluorine atom, and Z1 and Z2
Are independently of each other a 1,2-ethylene group, -CH = CH-
Or a covalent bond, and a represents 1 or 2.

In the formula (4), R2 represents a fluorine atom, an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. Any methylene group in the alkyl group or alkenyl group may be substituted with an oxygen atom, but no two or more methylene groups are continuously substituted with an oxygen atom. Ring B is 1,4-cyclohexylene, 1,4-phenylene or 1,3-dioxane-
2,5-diyl, ring C represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, ring D represents 1,4-cyclohexylene or 1,4-phenylene. Z3 represents a 1,2-ethylene group, -COO- or a covalent bond, L5 and L6 each independently represent a hydrogen atom or a fluorine atom, and b and c each independently represent 0 or 1. Show.

In the formula (5), R3 has 1 to 10 carbon atoms.
Is an alkyl group, L7 is a hydrogen atom or a fluorine atom, and d is 0 or 1.

In the formula (6), R4 has 1 to 10 carbon atoms.
The alkyl group of, ring E and ring F are independently of each other 1,4-cyclohexylene or 1,4-phenylene, Z4 and Z5 are independently of each other -COO- or a covalent bond, Z6 represents -COO- or -C≡C-, L8 and L9 each independently represent a hydrogen atom or a fluorine atom, and Y2 represents a fluorine atom, OCF3, OCF.
2H, CF3, CF2H or CFH2, e, f
And g each independently represent 0 or 1.

In the formula (7), R5 and R6 are independently of each other an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms.
10 alkenyl groups are shown. In each case, any of the methylene groups may be substituted by an oxygen atom, but two or more methylene groups are not consecutively substituted by an oxygen atom. Ring G represents 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, Ring H represents 1,4-cyclohexylene or 1,4-phenylene, and Z7 is -C≡C. -, -CO
O-, 1,2-ethylene group, -CH = CH-C [identical to] C- or a covalent bond is shown, and Z8 is -COO- or a covalent bond.

In the formula (8), R7 and R8 are independently of each other an alkyl group having 1 to 10 carbon atoms or 2 to 2 carbon atoms.
10 alkenyl groups are shown. In each case, any of the methylene groups may be substituted by an oxygen atom, but two or more methylene groups are not consecutively substituted by an oxygen atom. Ring I is 1,4-cyclohexylene, 1,4-phenylene or pyrimidine-2,5-diyl, Ring J is 1,4-cyclohexylene, and one or more hydrogen atoms on the ring are substituted with fluorine atoms. 1,4-phenylene or pyrimidine-2,5-diyl, which is optionally substituted, and ring K is 1,4-cyclohexylene or 1,4-cyclohexylene.
4-phenylene, Z9 and Z10 independently of each other represent -COO-, 1,2-ethylene group or a covalent bond, and Z11 represents -CH = CH-, -C≡C-, -COO-.
Alternatively, it represents a covalent bond, and h represents 0 or 1.

More specifically, the liquid crystal composition contains at least one compound selected from the group consisting of formulas (1), (2) and (3), or General formulas (4), (5), (6),
A liquid crystal composition comprising at least one compound selected from the group consisting of (7) and (8),
Alternatively, as the first component, at least one compound selected from the group consisting of formulas (1), (2) and (3) is used.
Containing a type, as the second component, the general formula (4), (5),
A liquid crystal composition or the like characterized by containing at least one compound selected from the group consisting of (6), (7) and (8) is preferable.

As the compounds of the general formulas (1) to (3), the compounds represented by the formulas (1-1) to (3-53) can be preferably mentioned.

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

[Chemical 6]

[0051]

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[0052]

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[0053]

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[0054]

Embedded image (R1 has the same meaning as above)

The compounds of the general formulas (1) to (3) are compounds having a positive dielectric anisotropy value and are excellent in thermal stability and chemical stability, and particularly have a high voltage holding ratio or a specific resistance. It is an indispensable compound when preparing a liquid crystal composition for TFT, which requires high reliability such as a large value.

As the compounds of the general formulas (4) to (6), the compounds of the formulas (4-1) to (6-14) are preferable.

[0057]

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[0058]

[Chemical 12]

[0059]

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(R2 to R4 have the same meanings as described above) The compounds of the general formulas (4) to (6) have a positive dielectric anisotropy value and a large value, and particularly the purpose of reducing the threshold voltage. Used in. It is also used for the purpose of adjusting the viscosity, adjusting the refractive index anisotropy value, and expanding the nematic range such as increasing the clearing point. Further, it is also used for the purpose of improving the steepness of the threshold voltage.

As the compounds of the general formulas (7) and (8),
Preferably, the compounds of formulas (7-1) to (8-12) can be mentioned.

[0062]

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[0063]

Embedded image (R5 to R8 have the same meanings as described above) The compounds of the general formulas (7) and (8) are compounds having a negative or weakly positive dielectric anisotropy value. The compound of the general formula (7) is mainly used for the purpose of decreasing the viscosity or adjusting the refractive index anisotropy value. Further, the compound of the general formula (8) is used for the purpose of broadening the nematic range such as increasing the clearing point or adjusting the refractive index anisotropy value.

The surface subjected to the alignment treatment and the aligning agent regulate the alignment of the liquid crystal molecules, and may be either an inorganic substance or an organic substance. Generally, polyimide-based and polyamide-based resins are often used, but as an example,
Chisso Orientation Agents are particularly preferred, but not limiting. That is, any of the aligning agents can be used.

More specifically, as the aligning agent, an aligning agent having a structure represented by the following general formula (9) is preferable.

Embedded image

In the formula (9), X is a divalent aromatic group,
Y represents a tetravalent aromatic ring or an aliphatic ring having a 4-, 5- or 6-membered ring structure. Specific examples of X include formula (X1) to
The group shown by (X8) can be mentioned.

[0067]

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In the formula, R represents H or an alkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 3, and m represents 1 or 2. Specific examples of Y include formulas (Y1) to (Y11).
And the group represented by

[0069]

Embedded image In the formula, R represents H or an alkyl group having 1 to 10 carbon atoms,
n shows the integer of 0-4 and m shows 0 or 1. Further, other known liquid crystal display device configurations can be used.

[0070]

EXAMPLES The present invention will now be specifically described with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples. Synthesis of silicon-containing polyamic acid solution consisting of reaction products of tetracarboxylic dianhydride, diamine and aminosilicon compound

Synthesis Example 1 A 500 ml separable flask equipped with a thermometer and a stirring blade was purged with nitrogen, and then 3,3′-diaminodiphenyl sulfone (hereinafter abbreviated as “DDS”) 4.85 g, 3
-Aminopropyltriethoxysilane (hereinafter "APS
Abbreviated as “E”) 43.22 g, and then dehydration-purified diethylene glycol dimethyl ether (hereinafter referred to as “D”).
Abbreviated as “G”) 210 g, and stirred at room temperature for DD
S and APSE were dissolved. Then, the flask was cooled in an ice bath, and when the temperature of the content liquid reached 10 ° C., 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid dianhydride (hereinafter abbreviated as “DSDA”) 4
1.93 g was added. When the temperature rise due to the exothermic reaction stopped, the ice bath was removed and the mixture was stirred at room temperature for 8 hours to obtain a pale yellow transparent silicon-containing polyamic acid solution. The rotational viscosity of this solution was 9 mPa · s. Here, the rotational viscosity is an E-type viscometer (trade name; VISCONIC END,
It is the viscosity measured at 25 ° C. using Tokyo Keiki Co., Ltd. (the same applies hereinafter).

Synthesis Example 2 APSE 49.76 was prepared using the same apparatus and method as in Synthesis Example 1.
g, and then 210 g of dehydrated and purified DG,
The APSE was dissolved by stirring at room temperature. Then, the flask was cooled with an ice bath, and when the temperature of the content liquid reached 10 ° C, 40.24 g of DSDA was added. When the temperature rise due to the exothermic reaction stopped, the ice bath was removed and the mixture was stirred at room temperature for 8 hours to obtain a pale yellow transparent silicon-containing polyamic acid solution. The rotational viscosity of this solution was 6 mPa · s.

Synthesis Example 3 Using the same device and method as in Synthesis Example 1, 4.36 g of DDS,
DG which was dehydrated and purified after charging 38.87 g of APSE
210 g was charged and stirred at room temperature to dissolve DDS and APSE. Then cool the flask in an ice bath,
When the temperature of the content liquid reached 10 ° C., 46.77 g of 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride was added. When the temperature rise due to the exothermic reaction stopped, the ice bath was removed and the mixture was stirred at room temperature for 8 hours to obtain a pale yellow transparent silicon-containing polyamic acid solution. The rotational viscosity of this solution was 7.5 mPa · s.

Synthetic Example 4 Using the same apparatus and method as in Synthetic Example 1, 4.93 g of DDS,
p-aminophenyltrimethoxysilane (hereinafter “APM
Abbreviated as "S") 42.38 g was charged, and then 210 g of dehydrated and purified DG was charged and stirred at room temperature to obtain DDS, A
PMS was dissolved. Then, the flask was cooled in an ice bath, and when the temperature of the content liquid reached 10 ° C, DS
42.68 g of DA was added. When the temperature rise due to the exothermic reaction stopped, the ice bath was removed and the mixture was stirred at room temperature for 8 hours to obtain a pale yellow transparent polyamic acid solution. The rotational viscosity of this solution was 11 mPa · s.

Synthesis Example 5 Using the same apparatus and method as in Synthesis Example 1, 14.8 g of DDS,
DG dehydrated and purified after charging 13.19 g of APSE
240 g was charged and stirred at room temperature to dissolve DDS and APSE. Then cool the flask in an ice bath,
When the temperature of the content liquid reaches 10 ° C, DSDA3
2.1 g was added. When the temperature rise due to the exothermic reaction stopped, the ice bath was removed and the mixture was stirred at room temperature for 8 hours to obtain a pale yellow transparent polyamic acid solution. The rotational viscosity of this solution was 17.2 mPa · s.

Example 1 In a 500 ml separable flask containing nitrogen and replaced with a stirring blade, 100 g of the silicon-containing polyamic acid solution obtained in Synthesis Example 1, 30 g of Epicoat 191P (produced by Yuka Shell Epoxy Co., Ltd.), and anhydrous Trimellitic acid 16.95
g, 3-glycidoxypropyltrimethoxysilane 3.
85 g and 24.05 g of dehydrated and purified DG were charged and stirred at room temperature to uniformly dissolve them. Then Byk-344
0.17 g (manufactured by BYK Chemie Co., Ltd.) was added, the mixture was stirred at room temperature for 1 hour, and filtered with a membrane filter having a pore size of 0.22 μm to prepare a coating solution. The coating solution was spin-coated on a glass substrate and a color filter substrate, and then prebaked at 80 ° C. for 3 minutes on a hot plate to form a coating film. Then, the coating film was cured by heating in an oven from 150 ° C. to 230 ° C. for 20 minutes and then at 230 ° C. for 1 hour to obtain a cured film having a thickness of 3 μm. About the cured film thus obtained, transparency,
The following characteristics were evaluated with respect to heat resistance, chemical resistance, flatness, adhesion and spatter resistance. Table 1 shows the results of these evaluations.
Shown in

[Evaluation Method] Transparency: In the obtained glass substrate with a cured film, a spectrophotometer (trade name: U-3210, manufactured by Hitachi Ltd.)
The transmittance of the cured film alone at 400 to 800 nm was measured by. Minimum transmittance at this time (that is, wavelength 400n
When the rate of change in transmittance (m) exceeds 95%, ○, 9
The case of 0 to 95% was marked with Δ, and the case of less than 90% was marked with x.

Heat resistance: After reheating the obtained glass substrate with a cured film at 250 ° C. for 1 hour, the rate of change in the residual film after heating and the rate of change in transmittance before and after heating (wavelength 4
The change rate of the transmittance at 00 nm) was measured. When the residual film rate after heating exceeded 95%, it was evaluated as ◯, when 90 to 95% was evaluated as Δ, and when it was less than 90% as ×. The case where the rate of change in transmittance before and after heating was less than 5% was marked with ◯, the case of 5 to 10% was marked with Δ, and the case where it exceeded 10% was marked with x.

Chemical resistance: The obtained glass substrate with a hardened film was immersed in a 5% aqueous sodium hydroxide solution at 30 ° C. for 30 minutes (hereinafter abbreviated as NaOH treatment), and in a 47% hydrobromic acid aqueous solution 45. Immersion treatment at 15 ° C for 15 minutes (hereinafter abbreviated as HBr treatment) and 40 ° C in N-methylpyrrolidone
After 30 minutes of immersion treatment (hereinafter abbreviated as NMP treatment) separately, the residual film rate after each treatment and the change rate of the transmittance before and after each treatment with respect to the film thickness before each treatment were measured. When the residual film rate after each treatment exceeded 95%, it was evaluated as ◯, when 90 to 95% was evaluated as Δ, and when it was less than 90% as ×. When the rate of change in transmittance before and after each treatment is less than 5%, ○: 5 to 10%
When it was, the case was Δ, and when it exceeded 10%, it was shown as x.

Flatness: A stylus-type film thickness meter (trade name;
alpha-step200, TENCOR INST
RUMENTS). The maximum value of the step between R, G, and B pixels including the black matrix (hereinafter,
(Abbreviated as maximum roughness) is ○ when less than 0.05 μm, Δ when it is 0.05 to 0.1 μm, 0.1 μm
When the value exceeded, it was marked as x. The color filter substrate used was an electrodeposition color filter having a maximum roughness of about 0.8 μm (hereinafter abbreviated as electrodeposition CF) and a printing color filter having a maximum roughness of about 0.2 μm (hereinafter, printing CF).
Abbreviated).

Adhesion: The obtained cured glass substrate with a cured film was subjected to a pressure cooker test (hereinafter PCT) for 24 hours under the conditions of 120 ° C., 100% and 0.2 MPa.
(Hereinafter, abbreviated as "treatment"), a cured film was subjected to a tape-shaped test (JIS-K-5400), and the remaining number was counted. When the remaining number / 100 is 100/100, it is ◯, when it is 99/100 to 90/100, it is Δ,
The case where it was 89/100 or less was marked with x.

Sputter resistance: When the ITO film was formed on the cured film by sputtering at 240 ° C. so that a resistance value of 10 Ω / cm ² was obtained on the obtained glass substrate with the cured film, the film wrinkled. The presence or absence of occurrence was investigated. The case where there was no wrinkle was marked with ◯, and the case where wrinkle occurred was marked with x.

Example 2 A poly (amic acid) solution 10 obtained in Synthesis Example 1 was placed in a 500-ml separable flask containing nitrogen and replaced with a stirring blade.
0 g, Epicoat 828 (produced by Yuka Shell Epoxy Co., Ltd.)
30 g, 15.3 g of trimellitic anhydride, 3.77 g of 3-glycidoxypropyltrimethoxysilane and 42.95 g of dehydrated and purified DG were charged and stirred at room temperature to uniformly dissolve them. Next, 0.19 g of Byk-344 (manufactured by BYK Chemie Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour,
A coating solution was prepared by filtering with a membrane filter having a pore size of 0.22 μm. Then, a cured film was formed in the same manner as in Example 1 and its characteristics were evaluated. Table 1 shows the evaluation results.

Example 3 The polyamic acid solution 10 obtained in Synthesis Example 2 was placed in a 500 ml separable flask containing nitrogen and replaced with a stirring blade.
0g, Araldite CY184 (Japan Ciba Geigy Co., Ltd.)
60 g), trimellitic anhydride 33.9 g and dehydrated and purified DG 53.9 g were charged and stirred at room temperature to uniformly dissolve. Then, 0.25 g of Byk-344 (manufactured by BYK Chemie Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour,
A coating solution was prepared by filtering with a membrane filter having a pore size of 0.22 μm. Then, a cured film was formed in the same manner as in Example 1 and its characteristics were evaluated. Table 1 shows the evaluation results.

Example 4 A coating solution was prepared in the same manner as in Example 1 except that the polyamic acid solution obtained in Synthesis Example 3 was used instead of the polyamic acid solution obtained in Synthesis Example 1. Prepared. Then, a cured film was formed in the same manner as in Example 1 and its characteristics were evaluated. Table 1 shows the evaluation results.

Example 5 A coating solution was prepared in the same manner as in Example 1 except that the polyamic acid solution obtained in Synthesis Example 4 was used instead of the polyamic acid solution obtained in Synthesis Example 1. Prepared. Then, a cured film was formed in the same manner as in Example 1 and its characteristics were evaluated. Table 1 shows the evaluation results.

Comparative Example 1 The polyamic acid solution obtained in Synthesis Example 1 was treated with a pore size of 0.22 μm.
m membrane filter to prepare a coating solution. Then, a cured film was formed in the same manner as in the example, and its characteristics were evaluated. Table 1 shows the evaluation results.

Comparative Example 2 The polyamic acid solution 10 obtained in Synthesis Example 5 was placed in a 500 ml separable flask containing a stirring blade and purged with nitrogen.
0g, Epicoat 191P (Yukaka Shell Epoxy Co., Ltd.)
20 g, Trimellitic anhydride 11.3 g, 3-glycidoxypropyltrimethoxysilane 2.57 g and dehydrated and purified DG 15.27 g were charged and stirred at room temperature to uniformly dissolve. Next, 0.15 g of Byk-344 (manufactured by BYK Chemie Co., Ltd.) was added, the mixture was stirred at room temperature for 1 hour, and filtered with a membrane filter having a pore diameter of 0.22 μm to prepare a coating solution. Then, a cured film was formed in the same manner as in Example 1 and its characteristics were evaluated. Table 1 shows the evaluation results.

[0089]

[Table 1]

As is clear from the results shown in Table 1, the cured films of Examples 1 to 5 are balanced in all of transparency, heat resistance, chemical resistance, flatness, adhesion and spatter resistance. It is clear that there is no problem in practical use. On the other hand, a cured film obtained only from the polyamic acid solution containing no epoxy resin and no epoxy curing agent in Comparative Example 1 and Comparative Example 2
Diamine / aminosilicon compound ≦ 0.4 (molar ratio)
A cured film obtained from a coating solution using a polyamic acid solution that does not satisfy is inferior in transmittance, particularly in flatness,
It is unsuitable as a color filter protective film and a transparent insulating film.

[0091]

The cured film obtained by heating and curing the thermosetting resin composition of the present invention is well balanced in transparency, heat resistance, chemical resistance, flatness, adhesion and spatter resistance. It is a very practical product. In particular, it is useful as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

Claims (9)

[Claims] 1. A resin composition comprising a polycarboxylic acid comprising a reaction product of tetracarboxylic dianhydride, a diamine and an aminosilicon compound (hereinafter abbreviated as silicon-containing polyamic acid), an epoxy resin, an epoxy curing agent and a solvent. It is characterized in that the epoxy resin is 50 to 250 parts by weight with respect to 100 parts by weight of the silicon-containing polyamic acid, and the epoxy curing agent is 1 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. Thermosetting resin composition. 2. The silicon-containing polyamic acid comprises X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of an aminosilicon compound so that the relationships of the following formulas (101) and (102) are established. The thermosetting resin composition according to claim 1, which is obtained by reacting in various ratios. 1.8 ≦ Z / (X−Y) ≦ 2 (101) Y / Z ≦ 0.4 (102) 3. A cured film obtained by heating and curing the thermosetting resin composition according to claim 1. 4. A color filter using the cured film according to claim 3 as a protective film. 5. A liquid crystal display device using the color filter having the cured film according to claim 3 as a protective film. 6. A solid-state imaging device using the color filter having the cured film according to claim 3 as a protective film. 7. A liquid crystal display device, wherein the cured film according to claim 3 is used as a transparent insulating film formed between a TFT and a transparent electrode. 8. A liquid crystal display device, wherein the cured film according to claim 3 is used as a transparent insulating film formed between a transparent electrode and an alignment film. 9. An LED light-emitting body using the cured film according to claim 3 as a protective film.