JPH0583580B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel heat-resistant resin composition. [Prior Art] In recent years, electronic components are particularly required to be highly integrated and highly reliable. Along with this, there is a desire to develop polymeric materials with excellent heat resistance, adhesiveness, moldability, and 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. These resins have excellent impact resistance, mechanical strength, solvent resistance, etc. in addition to heat resistance, and are attracting attention as polymeric electronic materials, but they have drawbacks in moldability, 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. [Problems to be Solved by the Invention] However, the polyimide resins, polyamideimide resins, and polyamide resins that have been proposed so far have a problem that they have low compatibility with epoxy resins and are not uniformly mixed with the desired composition. However, it has not been possible to obtain a polymer composition that simultaneously satisfies the above-mentioned properties required for electronic parts. Therefore, it is currently desired to realize a polymer 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 represented by the following general formula (). repeat unit

[Formula] (wherein, R represents a phenylene group or a C ₁ to _{C 12} alkylene group which may be substituted with a lower alkyl group), 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, and the following general formula ()

[Formula] (In the formula, Ar represents a tetravalent aromatic organic group,
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 polyamide-imide resin which is a polycondensate with a tetracarboxylic dianhydride and has an intrinsic viscosity of 0.1 to 5.0 dl/g, preferably 0.2 to 3.0 dl/g.
60 to 99% by weight, and (b) epoxy resin 1 to 40% by weight. In this specification, the intrinsic viscosity means a value measured at 30°C of an N-methyl-2-pyrrolidone solution with a resin concentration of 0.5 g/dl. The polyamide-imide resin used in the present invention has a main chain consisting of repeating units represented by the above general formula (), and has an intrinsic viscosity of 0.01 to 3.0 dl/g,
In addition, it can be produced by a polycondensation reaction between a polyamide having amino groups at both ends of the main chain and the tetracarboxylic dianhydride shown in () above. The above polyamide used as a raw material has the following general formula () H ₂ NR-NH ₂ () (wherein R is a phenylene group which may be substituted with a lower alkyl group or C ₁ - represents a _C12 alkylene group) and the following general formula ()

It can be obtained by subjecting an aromatic dicarboxylic acid represented by the formula to a polycondensation reaction using a known method. In that case, examples of diamine compounds represented by the above general formula () that can be used include the following compounds. m-phenylenediamine, p-phenylenediamine, metatolylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl thioether, 3,
3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, 3,3'-diaminodiphenyl thioether, 4,4'-diaminobenzophene Non, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,
3'-methoxy-4,4'-diaminodiphenylmethane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 4,4'-diaminodiphenyl sulfoxide ,
4,4'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenyl sulfone, benzidine, 3,
3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, hexamethylene diamine, heptamethylene diamine, tetramethylene diamine, p-xylylene diamine, m-xylylene diamine, 3 -Methylheptamethylenediamine, etc. Further, the aromatic dicarboxylic acids represented by the above general formula () that can be used for polycondensation with these diamine compounds include, for example, 3-hydroxyphthalic acid, 4-hydroxyphthalic acid, 2-hydroxyphthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 3-hydroxyterephthalic acid,
etc. can be mentioned. On the other hand, examples of the tetracarboxylic dianhydride derivative represented by the above general formula () include pyromellitic dianhydride, 2,3,6,7-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)propane dianhydride, 3,4,
Examples include 3',4'-benzophenonetetracarboxylic dianhydride and butanetetracarboxylic dianhydride. The reaction between a polyamide whose main chain is composed of repeating units represented by the above general formula () and has amino groups at both ends of the main chain and a tetracarboxylic dianhydride represented by the above general formula () can be carried out using the known method. This can be done using a 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 inert polar organic solvents include N, N
-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone,
Examples include hexamethylphosphoric triamide. Examples of the imidization method include a method of dehydration and ring closure by heating. Reaction temperature is 150-400℃, preferably 180-350℃
The reaction time is 30 seconds to 10 hours, preferably 5 minutes to 5 hours. In the present invention, when the intrinsic viscosity of the polyamide-imide resin is lower than 0.1 dl/g, the film-forming ability is lost, and when it is higher than 5.0 dl/g, it becomes difficult to form a film uniformly, and the paint If it is, the viscosity is high, so there is a problem in handling. In the present invention, the preferred intrinsic viscosity range is 0.2 to 3.0 dl/g. Examples of the epoxy resin which is the other resin component of the heat-resistant resin composition of the present invention include bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, phenol novolak type epoxy resin, and bisphenol F type epoxy resin. , bisphenol S type epoxy resin, benzophenone type epoxy resin, naphthalene type epoxy resin, cyclopentadiene type epoxy resin, benzenetriol type epoxy resin, resorcinol sulfide type epoxy resin, isopropylbenzene type epoxy resin, fluorene type epoxy resin, modified Examples include epoxy resin. The heat-resistant resin composition of the present invention can be obtained by blending the above-mentioned polyamide-imide resin and the above-mentioned epoxy resin. It is necessary that the content be in the range of ~40% by weight.
When the blending ratio of polyamide-imide resin is lower than 60% by weight, heat resistance decreases, and when the blending ratio of polyamide-imide resin is lower than 60% by weight,
When the temperature is higher than , moldability and adhesiveness deteriorate.
A preferred blending ratio is 70 to 90% by weight of the polyamide-imide resin and 30 to 10% by weight of the epoxy resin. 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 the epoxy resin is dissolved in the same solvent or other solvent. What is necessary is just to dissolve it in the solvent and mix it into the above-mentioned 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. Also,
When the polyamide-imide resin is melted by heating, an epoxy resin can also be blended with the heated and melted polyamide-imide resin. Examples of solvents that dissolve polyamideimide resins and epoxy resins include N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylformamide.
-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, diethanolamine, triethanolamine, propanolamine, N,N-diethylbenzylamine. , 1,8-
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. Preferably, the mixture is heated for several hours. The heat-resistant resin composition of the present invention has excellent heat resistance, adhesiveness, 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 with reference to Examples. Examples 1 to 12 As polyamide-imide resins, those obtained by polycondensation of the tetracarboxylic dianhydrides shown in Table 1 and polyamides having the repeating units and intrinsic viscosity shown in Table 1 were used. . This is the first
The epoxy resin shown in the table was dissolved in N,N-dimethylformamide, and the resulting solution was cast onto a glass plate, heated at 60°C for 1 hour, and at 100°C for 2 hours.
A film was prepared by heat treatment at 200°C for 6 hours. The thermal decomposition start temperature of the obtained film was determined using a thermobalance (manufactured by Shinku Riko Co., Ltd.) at a heating temperature of 10°C/min.
The dielectric loss was measured using a TRS-10 type dielectric measuring device (manufactured by Ando Electric Co., Ltd.) after depositing an aluminum electrode, and the tensile strength was measured using a Tensilon tester (manufactured by Orientek Co., Ltd.). It was measured using Copper foil adhesive strength was determined by casting an N,N-dimethylformamide solution of polyamide-imide resin and epoxy resin onto copper foil, heating it at 60°C for 1 hour, and heating it at 100°C for 2 hours.
It was press-molded at 200° C. for 2 hours at 0.6 kg/cm ² , then heat treated at 200° C. for 4 hours, brought into thermal contact with a 40 μm thick copper foil, and measured using a peel strength tester.

【table】

〔Effect of the invention〕

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

Claims (1)

[Claims] 1 (a) Obtained by polycondensation of a diamine compound and an aromatic dicarboxylic acid, the main chain having the following general formula ()
It consists of a repeating unit represented by [formula] (wherein R represents a phenylene group or a C ₁ to C ₁₂ alkylene group which may be substituted with a lower alkyl group), and has an intrinsic viscosity of 0.01 to 3.0 dl/ g and having amino groups at both ends of the main chain, and the following general formula () [Formula] (where Ar represents a tetravalent aromatic organic group,
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. ) 60-99% by weight of a polyamide-imide resin which is a polycondensate with tetracarboxylic dianhydride and has an intrinsic viscosity of 0.1-5.0 dl/g, and (b) 1-40% by weight of an epoxy resin. A heat-resistant resin composition comprising: