JPS6411659B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyimide silane copolymer resin. The present invention provides a method for producing a resin that is particularly excellent in adhesiveness, abrasion resistance, and heat resistance and is useful as an electrical insulation material, various molding materials, coating materials, impregnation materials, and the like.

Conventionally, polyamide resin obtained by reacting diamine and tetracarboxylic dianhydride has been used as a resin-like material with excellent heat resistance for electrical insulation materials, but it has poor adhesive properties with substrates. It has poor adhesion to glass substrates, etc., and to improve this, certain coupling agents have been added, greatly limiting its range of use. The present invention provides a method for producing a polyimide silane copolymer resin that eliminates this drawback.

The present invention provides: (a) General formula In the formula, R is a divalent hydrocarbon group, R' is a monovalent hydrocarbon group, and R and R' may be the same or different), (b) aromatic diamine, and (c ) A polyimide silane compound in which a polyamic acid silane type intermediate obtained by reacting an aromatic tetracarboxylic dianhydride with a silane compound at a concentration of 0.1 to 50 mol% based on the total amount of the silane compound and aromatic diamine is dehydrated and ring-closed. This invention relates to a method for producing a polymer resin.

General formula used in the present invention Examples of silane compounds represented by the formula (wherein R is a divalent hydrocarbon group, R' is a monovalent hydrocarbon group, and R and R' may be the same or different) include: (Me represents a methyl group and Ph represents a phenyl group). This silane compound is used in a range of 0.1 mol% to 50 mol% based on the total amount of the silane compound and aromatic diamine. If it is used in an amount exceeding 50 mol %, it causes a decrease in molecular weight and heat resistance, and if it is less than 0.1 mol %, the properties such as the above-mentioned adhesiveness do not occur.

The aromatic diamine is not particularly limited and includes, for example, m-phenylene diamine, p-phenylene diamine, 4,4'-diaminodiphenylpropane,
4,4'-diaminodiphenylmethane (hereinafter referred to as "methylene dianiline"), benzidine, 4,
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'- Dimethoxybenzidine, 2,4-bis(β-amino-
t-butyl)toluene, bis(p-β-amino-
t-butylphenyl) ether, bis(p-β-
Methyl-o-aminopentyl)benzene, 1,3
-Diamino-4-isopropylbenzene, m-xylylene diamine, p-xylylene diamine, etc. are used, and these are used alone or in combination of two or more.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-
Diphenyltetracarboxylic dianhydride, 3,3′4,
4'-benzophenonetetracarboxylic dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1, 4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10
Examples include -perylenetetracarboxylic dianhydride and 4,4'-sulfonyldiphthalic dianhydride, and one or more of these may be used.

In the present invention, the total amount of the silane compound and aromatic diamine (diamine component) is set to be approximately equimolar to the aromatic tetracarboxylic dianhydride. Of the diamine components, silane compounds are
It is preferably 0.1 to 50 mol%.

In the practice of this invention, inert solvents are used. This solvent does not need to dissolve all three types of monomers.

Particularly preferred is one that dissolves the polyamic acid silane type intermediate produced. For example, one or two of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, etc. The above is used.

In the present invention, the silane compound, aromatic diamine and aromatic tetracarboxylic dianhydride are preferably first dissolved in the inert solvent as well as possible, and the reaction system is heated preferably at about 80°C or below, especially around room temperature or below. Stir while maintaining the temperature. As a result, the reaction proceeds rapidly, the viscosity of the reaction system gradually increases, and a polyamic acid silane type intermediate is produced.

This intermediate is preferably heated at a temperature between 100 and 350 °C for 30
When heat treated for minutes to 5 hours, dehydration and ring closure occur to obtain a polyimide silane copolymer resin. This dehydration
The ring-closing reaction may be carried out using acetic anhydride, phosphoric acid, or the like as a dehydrating agent. The above intermediate is poured onto a glass plate, etc., dried to form a film, dehydrated,
Ring closure may also be performed.

The polyimide silane copolymer resin obtained by the production method of the present invention has excellent adhesive properties, especially adhesive properties to substrates such as glass, so when it is used for liquid crystal alignment films, semiconductor protective films, etc. It is possible to effectively prevent separation from the substrate, moisture intrusion into the substrate interface, etc., and obtain a highly reliable product.

Examples of the present invention will be described below.

Example 1 In a 500 c.c. three-necked flask equipped with a thermometer, stirrer, and calcium chloride tube, 18.0 g of 4,4'-diaminodiphenyl ether, 3.0 g of di(aminopropoxy)diphenylsilane, and N - 300 g of methyl-2-pyrrolidone was added and stirred well.
To this was gradually added 32.2 g of 4,4'-benzophenonetetracarboxylic dianhydride. After addition,
Stirring was continued for 5 hours. Next, a part of this reaction solution (solution of the produced polyamic acid silane type intermediate) was collected and poured into water to precipitate, and its reduced viscosity η _sp/c
When measured, it was 0.70 dl/g (solvent dimethyl sulfoxide, concentration 0.1 g/100 c.c. solution, temperature 25°C).

The reaction solution was then applied onto a glass plate and dried to form a film, which was then treated at 300°C for 2 hours to obtain a polyimide silane type copolymer resin. This film had good adhesion to the glass substrate and was difficult to peel off from the glass substrate. In addition, it showed excellent adhesion and abrasion resistance, with no scratches up to 6H measured by the pencil hardness method.

Example 2 9.06 g of di(aminoethoxy)diphenylsilane, 13.9 g of 4,4'-diaminodiphenylmethane and 300 g of N,N-dimethylacetamide were placed in the same flask as in Example 1 and stirred well. To this were gradually added 10.9 g of pyromellitic dianhydride and 16.1 g of 4,4'-benzophenonetetracarboxylic dianhydride. After the addition was complete, stirring was continued for 5 hours. Next, using this reaction solution, a film was made in the same manner as in Example 1, and this was heated to 300°C.
After time treatment, a polyimide silane type copolymer resin film was obtained.

This film exhibited excellent adhesion and abrasion resistance similar to the film obtained in Example 1.

Claims (1)

[Claims] 1 (a) General formula A silane compound represented by the following formula: R represents a divalent hydrocarbon group, R' represents a monovalent hydrocarbon group, and R and R' may be the same or different. A polyamic acid silane type intermediate obtained by reacting (b) an aromatic diamine and (c) an aromatic tetracarboxylic dianhydride with a silane compound in an amount of 0.1 to 50 mol% based on the total amount of the silane compound and aromatic diamine. A method for producing a polyimide silane copolymer resin, which is characterized by subjecting the body to dehydration and ring closure.