JPH0446954A - Heat-resistant resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel heat-resistant resin composition.

[Conventional technology]

In recent years, electronic components are particularly required to be highly integrated and highly reliable. Along with this, heat resistance, adhesiveness, moldability,
There is a desire to develop polymeric materials with excellent electrical properties, and various proposals have been made.

Polyimide resins, polyamide-imide resins, polyamide resins, and the like are widely known as heat-resistant polymer materials. In addition to heat resistance, these resins have excellent impact resistance, mechanical strength, solvent resistance, etc., and are attracting attention as polymeric electronic materials.
There are problems with adhesion, etc. Therefore, in order to balance these advantages and disadvantages, consideration has been given to using it in combination with an epoxy resin to form a composite.

[Problem to be solved by the invention]

However, conventionally proposed polyimide resins, polyamideimide resins, and polyamide resins have a problem of low compatibility with epoxy resins and are not uniformly mixed with the desired composition. It has not been possible to obtain a polymer composition that satisfies the above requirements at the same time. Therefore, it is currently desired to realize a polymeric material that has excellent properties in all of heat resistance, adhesiveness, moldability, and electrical properties.

An object of the present invention is to provide a heat-resistant resin composition useful as a polymeric electronic material that has excellent heat resistance, adhesiveness, moldability, and electrical properties, and exhibits high precision and reliability.

[Means for Solving the Problems] The heat-resistant resin composition of the present invention is obtained by polycondensation of (a) a diamine compound and an aromatic dicarboxylic acid, and has a main chain having a repeating structure represented by the following general formula (1). unit (in the formula, R represents a phenylene group or a C1-CI2 alkylene group which may be substituted with a lower alkyl group), and has an intrinsic viscosity of 0.01 to 3.0 di) 7 g, and , a polyamide having amino groups at both ends of the main chain, and the following general formula (II) (wherein, Ar represents a tetravalent aromatic organic group, and each of the four carbonyl groups is directly attached to another carbon atom. and the carbonyl group of each month is bonded to the adjacent carbon atom in the Ar group. 0dj
7/g, preferably 02-3. It is characterized by consisting of 60-99% by weight of a polyamideimide resin having 7 g of OdN and (b) 1-40% by weight of an epoxy resin.

In addition, in this specification, the intrinsic viscosity refers to a resin concentration of 0.
5 g/dΩ of N-methyl-2-pyrrolidone solution
Means measured value in °C.

The polyamide-imide resin used in the present invention has a main chain consisting of repeating units represented by the above general formula (1),
Intrinsic viscosity 0. Old~3. A polyamide having Odρ/g and having amino groups at both ends of the main chain, and the above (II)
It can be produced by a polycondensation reaction with a tetracarboxylic dianhydride represented by:

The above polyamide used as a raw material has the following general formula (m) H2N-R-NH2(m) (wherein R is a phenylene group which may be substituted with a lower alkyl group or 01 to CI2). (represents an alkylene group) and an aromatic dicarboxylic acid represented by the following general formula (IV) H can be subjected to a polycondensation reaction by a known method.

In that case, examples of the diamine compound represented by the above general formula (m) that can be used include the following compounds. m-phenylene diamine, p-phenylene diamine, metatolylene diamine, 4,4'-diaminodiphenyl ether, 3,3 dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino diphenyl ether,
4.4'-diaminodiphenylthioether, 3.3'
-dimethyl-4,4'-diaminodiphenylthioether, 3.3'-jethoxy-4,4'-diaminodiphenylthioether, 3.3'-diaminodiphenylthioether, 4.4'-diaminobenzophenone, 3.1
'-dimethyl-4,4'-diaminobenzophenone, 3
．． 3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, L3'-methoxy-4,4'-diaminodiphenylmethane, 2,2''-bis(4-aminophenyl)propane, 2,2'-bis(3- aminophenyl)propane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone,
3.3”-diaminodiphenylsulfone, benzidine,
3.3'-dimethylbenzidine, 3.3'-dimethoxybenzidine, 3.3'-diaminobiphenyl, hexamethylene diamine, heptamethylene diamine, tetramethylene diamine, p-xylylene diamine, ■-xylylene diamine, 3-methylhebutamethylenediamine, etc.

Further, examples of the aromatic dicarboxylic acid represented by the above general formula (IV) that can be used for polycondensation with these diamine compounds include 3-hydroxyphthalic acid, 4-
Hydroxyphthalic acid, 2-hydroxyphthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid,
Examples include 2-hydroxyterephthalic acid, 3-hydroxyterephthalic acid, and the like.

On the other hand, examples of the tetracarboxylic dianhydride derivative represented by the above general formula (II) include pyromellitic dianhydride, 2.3,8.7-naphthalenetetracarboxylic dianhydride, 3.4. 3',4'-biphenyltetracarboxylic dianhydride, 2.3.2',3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3, 4-dicarboxyphenyl)sulfone dianhydride, 2,2-bis(3
, 4-dicarboxyphenyl)propanihydride, 3.
4.3', 4'-benzophenonetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, and the like.

The reaction between a polyamide whose main chain is composed of repeating units represented by the above general formula (I) and has amino groups at both ends of the main chain and a tetracarboxylic dianhydride shown by the above general formula (n) is as follows: This can be done using a known method. For example, the polyamide and tetracarboxylic dianhydride are reacted in an inert polar organic solvent at a temperature of -20 to 150°C, preferably 0 to 60°C for several tens of minutes to several days to produce polyamic acid. A polyamide-imide resin can be produced by further imidizing the polyamide-imide resin.

Examples of the inert polar organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-
Methyl-2-pyrrolidone, N-methylcaprolactam,
dimethyl sulfoxide, tetramethylurea, pyridine,
Examples include dimethyl sulfone and hexamethyl phosphoric triamide.

Examples of the imidization method include a method of dehydration and ring closure by heating.

The reaction temperature is 150-400°C, preferably 180-35°C.
The reaction time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours.

In the present invention, the intrinsic viscosity of the polyamideimide resin is o
If it is lower than , tdg/g, the film forming ability will be lost, and if it is higher than 5.0 dJl)/g, it will be difficult to form a film uniformly, and if it is made into a paint, it will have high viscosity, so it should be handled carefully. I have a sexual problem. In the present invention, the preferable intrinsic viscosity range is 0.2 to 3.0 dil/
It is g.

Examples of the epoxy resin that is the other resin component of the heat-resistant resin composition of the present invention include bisphenol A type epoxy resin, 0-cresol novolac type Evoquin resin, phenol novolac type Evoquin resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Epoxy resin, hensifenone type epoxy resin, naphthalene type epoxy resin,
Examples include cyclopentadiene type epoxy resin, vivensen i/liol type epoxy resin, resorcinol sulfy F type epoxy resin, isopropylbenzene type epoxy resin, fluorene type epoxy resin, modified epoxy resin, and the like.

The heat-resistant resin composition of the present invention is obtained by blending the above-mentioned polyamide-imide resin and the above-mentioned epoxy resin.
It is necessary that the amount of the epoxy resin be in the range of 1 to 40% by weight relative to 9% by weight of the epoxy resin.

If the blending ratio of polyamide-imide resin is lower than 60% by weight, heat resistance will decrease, and if it is higher than 99% by weight, moldability and adhesiveness will decrease.

The preferred blending ratio is that the polyamide-imide resin is 70%
~90% by weight, while epoxy resin has ~30~90% by weight.
It is in the range of 10% by weight.

In order to produce the heat-resistant resin composition of the present invention, the above-mentioned polyamide-imide resin is dissolved in a solvent, and the epoxy resin is directly dissolved in the above-mentioned polyamide-imide resin solution, or
Alternatively, the epoxy resin may be dissolved in the same solvent or another solvent and added to the polyamide-imide resin solution.

In that case, it is preferable that the solvent in which the polyamide-imide resin is dissolved and the solvent in which the epoxy resin is dissolved are the same. The solvent may be removed before use. When the epoxy resin is in liquid form, it can also be blended without being dissolved in a solvent. Moreover, when the polyamide-imide resin is melted by heating, an epoxy resin can also be blended with the polyamide-imide resin heated and melted.

Examples of the solvent for dissolving polyamideimide resin and epoxy resin include N,N-dimethylformamide, N
, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone,
Examples include hexamethylphosphoric triamide.

A curing accelerator can also be added to the heat-resistant resin composition of the present invention, if desired.

Examples of the curing accelerator include ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, dimethylaminopropylamine, cyclohexylaminopropylamine, monoethanolamine, jetanolamine, triethanolamine, propatoolamine, N, N-diethylbenzylamine, ■
, 8-diaza-bicyclo[5,4,0]undecane-
Examples include 7,1,1,3,3-tetramethylguanidine.

After blending the polyamide-imide resin and the epoxy resin, the heat-resistant resin composition of the present invention is prepared at a temperature of about 200°C for several minutes to form an interaction between the polyamide-imide resin and the epoxy resin. It is preferable to heat it for several hours.

The heat-resistant resin composition of the present invention has excellent heat resistance, adhesion, moldability, and electrical properties, so it is useful for applications such as films used at high temperatures, electric wire coatings, adhesives, paints, and laminates. It is.

〔Example〕

Next, the present invention will be explained in detail by way of examples.

Examples 1 to 12 As polyamide-imide resins, those obtained by polycondensation of tetracarboxylic dianhydrides shown in Table 1 and polyamides having the repeating units and intrinsic viscosity shown in Table 1 were used. This was dissolved in N,N-dimethylformamide together with the epoxy resin shown in Table 1, and the resulting solution was cast on a glass plate and heated at 60°C for 1 hour.
A film was prepared by heat treatment at 200°C for 2 hours and 6 hours at 200°C.

The thermal decomposition start temperature of the obtained film was measured using a thermobalance (manufactured by Shinku Riko Co., Ltd.) at a heating temperature of 10°C/ff1in, and the dielectric loss was measured at T
Measurements were made using an R3-1o type dielectric measuring device (manufactured by Ando Electric Co., Ltd.), and tensile strength was measured using a Tensilon tester (manufactured by Orientic Co., Ltd.).

Copper foil adhesive strength is determined by casting a solution of polyamideimide resin and epoxy resin in N,N-dimethylformamide onto copper foil.
1 hour at 60℃, 2 hours at ioo℃, 200℃, 0.6
kg/c- for 2 hours, heat treated at 200° C. for 4 hours, brought into thermal contact with a 40 mm thick copper foil, and measured using a beer strength tester.

The following margin [Effects of the invention] The heat-resistant resin composition of the present invention has excellent heat resistance, adhesiveness,
It has moldability and electrical properties, and is useful for applications such as films used at high temperatures, wire coatings, adhesives, paints, and laminated products, especially around semiconductor chips that exhibit high precision and reliability. It is useful as an adhesive material.

Claims (1)

[Claims] (1) (a) A repeating unit obtained by polycondensation of a diamine compound and an aromatic dicarboxylic acid, whose main chain is represented by the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (Formula (wherein, R represents a phenylene group which may be substituted with a lower alkyl group or an alkylene group of C_1 to C_1_2), and has an intrinsic viscosity of 0.01 to 3.0 dl/g,
and a polyamide having amino groups at both ends of the main chain,
The following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, Ar represents a tetravalent aromatic organic group, and each of the four carbonyl groups is directly bonded to a different carbon atom. and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar group.) A polycondensate with a tetracarboxylic dianhydride represented by 1. A heat-resistant resin composition comprising: 60 to 99% by weight of a polyamideimide resin having a polyamide-imide ratio of 1 to 40% by weight, and (b) 1 to 40% by weight of an epoxy resin.