JPH0441521A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance, adhesiveness, moldability and electrical properties and useful for wire coating, adhesives, coating materials, laminates, etc., by mixing a specified polyamideimide resin with an epoxy resin in a specified mixing ratio. CONSTITUTION:The title composition is prepared by mixing 60-99wt.% polyamideimide resin comprising repeating units of the formula [wherein Ar is a tetravalent aromatic organic group; the four carbonyl groups are directly bonded to different carbon atoms, and each pair of the carbonyl groups are bonded to adjacent carbon atoms of the Ar group; R is (lower alkyl-substituted) phenylene, or 1-1 C alkylene] and having an intrinsic viscosity of 9.1-5.0dl/g with 1-40wt.% epoxy resin (e.g. Epikote YL979, a product of Yuka-Shell Epoxy Co.).

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, polyamide-imide 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 to solve the problem]

One of the heat-resistant resin compositions of the present invention has - maximum [wherein A
r is a tetravalent aromatic organic group, each of the four carbonyl groups is directly bonded to another carbon atom, and the six pairs of carbonyl groups are bonded to adjacent carbon atoms in the Ar group, R represents a phenylene group or an alkylene group of 01 to CI2 which may be substituted with a lower alkyl group. ] and has an intrinsic viscosity of 0°1 to 5. Odfl/g, preferably 0.2-3.0d
It is characterized by being composed of 60 to 99% by weight of polyamideimide resin having a 1.1 liter/g and 1 to 40% by weight of epoxy resin.

Another heat-resistant resin composition of the present invention has - Maximum (1) [wherein, Ar is a tetravalent aromatic organic group, and each of the four carbonyl groups is directly bonded to another carbon atom, And, the six pairs of carbonyl groups are bonded to adjacent carbon atoms in the Ar group, R represents a phenylene group or a C1-CI2 alkylene group which may be substituted with a lower alkyl group, and R' is 2 2 having a valent aliphatic group or an aromatic ring
Indicates a valent organic group. ] The repeating units represented by are irregularly arranged, and −
The maximum repeating unit represented by (II) is the general formula (1)
It is contained in a molar ratio of 1/2 or less, preferably 1/4 to 1/loo, to the repeating unit represented by , and has an intrinsic viscosity of 0.1 to 5. Odff/g, preferably 0.2-3.
It is characterized by consisting of 60-99% by weight of polyamideimide resin having OdΩ/g and 1-40% by weight of epoxy resin.

(I) In this specification, the intrinsic viscosity refers to resin) JJl
jo, 5 g/dρ of N-methyl-2-pyrrolidone solution measured at 30°C.

The polyamide-imide resin composed of repeating units represented by -maximum (1) above used in the present invention is -maximum (1).
It can be obtained by polycondensation reaction of a diamine compound having amino groups at both ends represented by I[I)H (wherein R has the same meaning as above) and a tetracarboxylic dianhydride derivative. .

- Examples of diamine compounds represented by maximum (III) include the following compounds.

N,N''-bis(2-aminophenyl)-5-hydroxyisophthalamide, N,N'-bis(3-aminophenyl)-5-hydroxyisophthalamide, N,N'
-bis(4-aminophenyl)-5-hydroxyisophthalamide, N,N'-bis(2-aminophenyl)
-2 hydroxyterephthalamide, N, N'~bis(3
-aminophenyl)-2-hydroxyterephthalamide, N,N'-bis(4-aminophenyl)-2-hydroxyterephthalamide, N,N'-bis(2-aminophenyl)-2-hydroxyphthalamide, N , N'-bis(3-aminophenyl)-2-hydroxyphthalamide, N,N'-bis(4-aminophenyl)-2-hydroxyphthalamide, N,N'-bis(2-aminophenyl)- 3-Hydroxyphthalamide, N, N'-
Bis(3-aminophenyl)-3-hydroxyphthalamide, N,N'-bis(4-aminophenyl)-3-
Hydroxyphthalamide, N,N'-bis(4-amino-3,5-dimethylphenyl)-5-hydroxyisophthalamide, N,N'-bis(4-amino-3,5
-dimethylphenyl)-2-hydroxyterephthalamide, N,N'bis(4-amino-3,5-dimethylphenyl)-2-hydroxyphthalamide, N,N'-bis(4-amino-3,5- dimethylphenyl)-3-hydroxyphthalamide, N,N'-bis(4-amino-
n-butyl)-5-hydroxyisophthalamide, N,
N'-bis(6-amino-n-hexyl)-5-hydroquinisophthalamide]-1N, N'-bis(12-amino-n-dodecyl)-5-hydroquinisophthalamide, and the like.

Examples of the tetracarboxylic dianhydride derivatives to be polycondensed with the diamine compound include pyromellitic dianhydride, 2.3.6.7-naphthalene-1-lacarboxylic dianhydride, 3.4.3', 4'-biphenyltetracarboxylic dianhydride, 2.3.2', 3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxylic dianhydride) carboxyphenyl) sulfone dianhydride, 2,2-bis(3,4
-dicarboxyphenyl)propanihydride, 3.4.
Examples thereof include 3',4'-hensiphenotetracarboxylic dianhydride, butanetetracarboxylic dianhydride, and the like.

The polyamide-imide resin used in the present invention consisting of repeating units represented by the above-mentioned -maximum (1) and -maximum (II) has the above-mentioned -maximum (I[I) diamine and the following -maximum (IV) J (2N -R' -NH2(IV) (wherein R'
It can be produced by using a diamine compound represented by (has the same meaning as above) in combination, and polycondensing these with the above-mentioned tetracarphonic dianhydride derivative.

The diamine compound represented by the maximum (IV) is m-
Phenylene diamine, p-phenylenecyamine, metatrilenone amine, 4,4'-diaminodiphenyl ether, 3.3'-dimethyl-4,4'-diaminodiphenyl ether, 3.3'-aminosiphenyl ether, 3.4'-diaminone phenyl ether, 4.4'
-7aminophenylthioether, 3,3'dimethyl-4,4'-noaminodiphenylthioether, 3.3
'-Shedkin-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether,
4.4′-diaminobenzophenone, 3.3′-dimethyl-4.4′-diaminohensiphenone, 3.3′
-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy4,4'-diaminodiphenylmethane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-amino phenyl)propane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone,
3.3'-diaminodiphenylsulfone, benzidine, 3.3'-dimethylbenzidine, 8,3'-dimethoxybenzidine, 3.3'-diaminobiphenyl, hexamethylene diamine, heptamethylene diamine, tetramethylene diamine, p -xylylene diamine, m-xylylene diamine, 3-methylhbutamethylene diamine, etc.

The reaction between the diamine compound and the tetracarboxylic dianhydride derivative can be carried out using a known method. For example, in the case of a polyamideimide resin consisting of repeating units represented by general formula (1), tetracarboxylic dianhydride is added to 1 equivalent of the diamine compound represented by general formula (m) in an inert polar organic solvent. 0.8 to 1.
3 equivalents, -20-150°C, preferably 0-60°C
It can be produced by reacting at a temperature of .degree. C. for several tens of minutes to several days to produce a polyamic acid, followed by imidization. In addition, the above general formula (I) and general formula (
In the case of a polyamide-imide resin consisting of repeating units represented by II), it can be produced by combining the diamine compound represented by the above general formula (m) with the diamine compound represented by the above general formula (IV). . In that case, the ratio of the diamine compound represented by general formula (IV) to general formula (1) may be set to a molar ratio of 1/2 or less, preferably 1/4 to 1/100.

Examples of inert polar organic solvents include N,:J-dimethylformamide, N,N-dimethylacetamide, N
-Methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethyllinic acid triamide, and the like.

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

The reaction temperature is 151) to 400°C, preferably 180 to 3
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
If it is lower than 0.1 clQ/g, it will lose its ability to form a film, and if it is higher than 5.0 dJ77g, it will be difficult to form a uniform film, and if it is made into a paint, it will have a high viscosity, making it difficult to handle. There is a problem. In the present invention, the preferred intrinsic viscosity range is 0.2 to 3.0 c
al 7g.

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 epoxy resin, phenol novolac type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Epoxy resin, benzophenone type epoxy resin, naphthalene type epoxy resin,
Examples include cyclopentadiene type epoxy resin, bibenzenetriol type epoxy resin, resorcinol sulfide type epoxy resin, isopropylbenzene type epoxy resin, fluorene type epoxy resin, and modified epoxy resin.

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.

When the proportion of the polyamide-imide resin is lower than 60% by weight, heat resistance decreases, and when it exceeds 99% by weight, moldability and adhesiveness 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 lOm2%.

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 for dissolving the polyamide-imide resin and the solvent for dissolving the epoxy resin are the same. The solvent may be removed before use. If the epoxy resin is in liquid form, it can be blended without being dissolved in a solvent. Furthermore, when the polyamide-imide resin is melted by heating, an epoxy resin may be blended with the heated and melted polyamide-imide resin.

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, hexamethylphosphoric triamide, and the like.

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,
1.8-diazabicyclo[5,4,0]undecane-
Examples include 7, L, 1, 3,3-tetramethylguaninone.

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. Preferably, the mixture is heated for several hours.

The heat-resistant resin composition of the present invention has excellent heat resistance, adhesion, moldability, and electrical properties, so it can be used in, for example, films used at high temperatures, wire coatings, adhesives, coatings, and laminated products. Useful.

〔Example〕

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

Examples 1 to 14 N,N-dimethylformamide solutions of polyamideimide resins and epoxy resins shown in Table 1 were cast onto a glass plate, and heated at 60°C for 1 hour, 100°C for 2 hours, and 200°C. A film was prepared by heat treatment for 6 hours.

The thermal decomposition initiation temperature of the obtained film was measured using a thermobalance (manufactured by Shinku Riko Co., Ltd.) under the condition of a heating temperature of 10°C/min, and the dielectric loss was measured after evaporating an aluminum electrode.
A using a 5-10 type dielectric measurement device (manufactured by Ando Electric Co., Ltd.)
The tensile strength was measured using a Tensilon tester (manufactured by Orientic Co., Ltd.).

Copper foil adhesive strength was determined by casting an N,N-/methylformamide solution of polyamideimide resin and epoxy resin onto copper foil.
60°C for 1 hour, 100°C for 211. 'j between, 20
0°C10.6kg/cn? Press molded for 2 hours,
Further, it was heat treated at 200°C for 4 hours, brought into thermal contact with a copper foil having a thickness of 1 m at 40°C, 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 (2)

[Claims] (1) The following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, Ar is a tetravalent aromatic organic group, and each of the four carbonyl groups is a different carbon atom. and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar group, and R represents a phenylene group or an alkylene group of C_1 to C_1_2 which may be substituted with a lower alkyl group. ] 60 to 99% by weight of a polyamideimide resin having an intrinsic viscosity of 0.1 to 5.0 dl/g, and epoxy resin 1 to 4
A heat-resistant resin composition comprising 0% by weight. (2) General formula (1) and general formula (II) below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, Ar is a tetravalent is an aromatic organic group in which 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, and R is a lower alkyl group. represents a phenylene group or an alkylene group of C_1 to C_1_2 which may be substituted by R', and R' represents a divalent aliphatic group or a divalent organic group having an aromatic ring. ] The repeating units represented by are arranged irregularly, and the repeating units represented by the general formula (II) have the general formula (I)
60-99% by weight of a polyamide-imide resin which is contained in a molar ratio of 1/2 or less with respect to the repeating unit represented by and has an intrinsic viscosity of 0.1-5.0 dl/g, and 1-40% by weight of an epoxy resin A heat-resistant resin composition comprising: