JPH0320129B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a heat-resistant resin composition, a prepreg, and a molding material used in a highly heat-resistant insulating material. [Background technology] Conventionally, resin materials used as insulating materials in the electronics field include epoxy resins and phenol resins for varnishes for laminated boards, electronics, etc. for semiconductor packages, structural materials for electrical appliances, sliding materials, etc.
Epoxy resins, phenolic resins, alkyd resins, etc. are used as electrical molding materials. However, these resins cannot sufficiently meet the demand for high heat resistance of insulating materials against heat generation during the mounting process or during use, which is a result of the high-density packaging of electronics-related equipment in recent years, and problems arise. It came. In order to solve these problems from the viewpoint of materials, heat-resistant materials such as imide resins and amide-imide resins for use as varnishes for laminates and silicone resins for use as molding materials are currently being developed and put into practical use. However, all of these heat-resistant resin materials have difficulties in processability, and there are few that can be used freely for purposes such as varnish for laminates or molding materials, and new heat-resistant resins that can be used in a wide range of applications are needed. It is hoped that the emergence of [Object of the Invention] The present invention provides a heat-resistant resin composition that has excellent insulation properties and heat resistance that enable high-density mounting of electronic components, and is suitable for both varnish use for laminates and molding material use. , aims to provide prepreg and molding materials. [Disclosure of the Invention] In order to achieve the above objects, the following three inventions were completed. That is, in the first invention, a prepolymer is added to a compound having at least two epoxy groups in the molecule.
(A) is a heat-resistant resin composition, and the prepolymer (A) is an intermediate (BT) obtained by reacting a maleimide compound and a diamine in advance.
A second heat-resistant resin composition characterized by using a composition obtained by reacting a and an unsaturated bis-imide.
The invention is a prepreg made by impregnating a base material with a heat-resistant resin composition, and the heat-resistant resin composition is a prepreg prepared by blending a prepolymer (A) with a compound having at least two epoxy groups in the molecule. The prepolymer (A) is a heat-resistant resin composition consisting of
A third aspect of the present invention is a prepreg characterized by using a prepreg obtained by reacting an intermediate (B) obtained by reacting a maleimide compound and a diamine in advance with an unsaturated bisimide, and a third invention provides a heat-resistant resin composition, The molding material is a molding material containing at least a filler, and the heat-resistant resin composition is a heat-resistant resin composition containing a prepolymer (A) and a compound having at least two epoxy groups in the molecule. ,
The prepolymer (A) is a molding material characterized by using a product obtained by reacting an intermediate (B) obtained by reacting a maleimide compound and a diamine in advance with an unsaturated bis-imide. . These inventions will be explained in detail below. Here, the epoxy compound is not particularly limited as long as it is a compound having at least two epoxy groups in the molecule, but it is preferable to use the following epoxy resins having an epoxy equivalent of 100 to 4,000. Hisphenol epoxy resins, alicyclic epoxy resins, polyphenol epoxy resins, nitrogen-containing epoxy resins, novolak epoxy resins, and halides of the above-mentioned epoxy resins. The prepolymer (A) used in this invention is usually produced as follows. That is, an intermediate (B) obtained by reacting a maleimide compound represented by the following general formula () with a diamine compound represented by the following general formula () in advance, and an intermediate (B) represented by the following general formula (). It is obtained by reacting with unsaturated bis-imide. (In the formula, R ₁ is a divalent organic group) H ₂ N−R ₂ −NH ₂ … () (In the formula, R ₂ is a divalent organic group) (wherein R ₃ is a divalent organic group) where the symbols R ₁ , R ₂ , R ₃ can be the same or different and can also be a straight chain with less than 13 carbon atoms. a chain or branched alkylene group, a cyclic alkylene group having 5 or 6 carbon atoms in the ring, or a heterocyclic group containing at least one of O, N and S atoms;
Alternatively, it can also be phenylene or a polycyclic aromatic group. These various groups may have substituents that do not give rise to unnecessary side reactions under the reaction conditions. The symbols R ₁ , R ₂ , R ₃ can also represent numerous phenylene groups or alicyclic groups. In this case, adjacent phenylene groups or alicyclic groups may be bonded directly or via divalent atoms or groups. Maleimide compound represented by formula ()
Preferred examples of R ₁ include: Preferred examples of the diamine represented by formula () include the following. 4,4'-diaminodicyclohexylmethane,
1,4'-diaminocyclohexane, 2,6-diaminopyridine, metaphenylenediamine, paraphenylenediamine, 4,4'-diamino-diphenylmethane, 2,2-bis-(4-aminophenyl)
Propane, benzidine, 4,4'-diaminophenyl oxide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, bis-(4-aminophenyl)diphenylsilane, bis-(4- Aminophenyl) methylphosphine oxide, bis-(3-aminophenyl)methylphosphine oxide, bis-(4
-aminophenyl)-phenylphosphine oxide, bis-(4-aminophenyl)pheniramine, 1,5-diaminonaphthalene, metaxylylene diamine, paraxylylene diamine, 1,1
-bis-(para-aminophenyl)phthalane and hexamethylene diamine. Preferred examples of the unsaturated bis-imide represented by formula () include the following. Maleic acid N・N'-ethylene-bis-imide,
Maleic acid N・N′-hexamethylene bis-imide, maleic acid N・N′-metaphenylene bis-imide, maleic acid N・N′-paraphenylene bis-imide, maleic acid N・N′-4・4 ′−
Diphenylmethane-bis-imide [also called N-N'-methylenebis (N-phenylmaleimide)], maleic acid N-N'-4,4'-diphenyl ether-bis-imide, maleic acid N-N'-
4,4′-diphenylsulfon-bis-imide,
Maleic acid N・N′-4・4′-dicyclohexylmethane-bis-imide, maleic acid N・N′-α・
α′-4・4′-dimethylenecyclohexane-bis-
Imide, maleic acid N・N'-methaxylylene-
bis-imide, and N.N'-diphenyl maleate cyclohexane-bis-imide. Intermediate (B) of the present invention can be obtained by the reaction of the maleimide compound and diamine as described above, and it is preferable that the molar ratios of the components are as shown below. That is, the diamine should be 10 to 50 mol% relative to the maleimide compound 50 to 90 mol%, and more preferably,
60-70 mol% maleimide compound to 30% diamine
~40 mol%. When the molar ratio of maleimide compounds exceeds 90 mol%, an intermediate in which four maleimide compounds are bonded to two amino groups in the diamine is obtained, and when this intermediate is used, subsequent prepolymer synthesis The reaction tends to be difficult to proceed and the yield of intermediates tends to be low. On the other hand, when the ratio of the maleimide compound is less than 50 mol%, the amount of maleimide compound bonded to one molecule of the intermediate diamine to be synthesized is 0 to 50% by mole.
1 molecule, and when this intermediate is used,
It is difficult to obtain sufficient heat resistance for the resin composition. In contrast, the proportion of maleimide compounds is 50 to 90 mol%.
An intermediate (B) in which 1 to 3 molecules of a maleimide compound are bonded to one molecule of diamine is synthesized, and this intermediate (B) has excellent heat resistance, moldability, and flexibility. A sticky resin composition is obtained. The prepolymer (A) of this invention is obtained by the reaction of the intermediate (B) as described above and an unsaturated bis-imide, and the components are mixed in the ratio shown below. It is preferable. That is, the combination of intermediate (B) and unsaturated bis-imide used in the reaction is such that the number of moles of unsaturated bis-imide per mole of intermediate (B) is It is preferable to set the ratio to be approximately equal to the number of moles of active hydrogen. The reaction of the intermediate (B) and the unsaturated bis-imide to form the prepolymer (A) is carried out either in the hot melt state or in solution using an inert solvent. Examples of inert solvents used when the reaction is carried out in a solution state include N
-Methylpyrrolidone, dimethylformamide, dimethylacetyamide, etc. When synthesizing prepolymer (A) in a high-temperature molten state, the temperature usually needs to be 150°C or higher, and when synthesizing prepolymer (A) in a solution state, the temperature is not particularly limited. , preferably in the range of 50 to 200°C. The heat-resistant resin composition of the first invention is obtained by blending the above-mentioned prepolymer (A) with the above-mentioned epoxy compound. The prepreg according to the second invention is obtained by making the heat-resistant resin composition according to the first invention into a solution state with an inert solvent and impregnating it into a base material. In this case, the type of base material is not particularly limited, but
The following are preferred. The base material made of inorganic material is fiber or cloth made of glass, quartz, alumina, graphite, carbon, etc. Examples of the base material made of organic material include aromatic polyacid fibers, such as Dupont's Kevlar fiber, Nomex fiber, and their respective cloths. The molding material according to the third invention is obtained by blending at least a filler with the heat-resistant resin composition according to the first invention, and, if necessary, blending stabilizers, pigments, and other usual compounding materials used for forming molding materials. It can be obtained by In this case, the type of filler is not particularly limited, but the following are preferred. Fillers made of inorganic materials include fibers or powders made of glass, quartz, alumina, graphite, carbon, etc. Fillers made of organic materials include the above-mentioned Kevlar fibers, Nomex fibers, and thermosetting resin powders such as phenol novolak. Next, each example of the first invention, the second invention, and the third invention will be described, but prior to that, the method of synthesizing the intermediate will be explained first. Intermediate (B) was synthesized and measured as follows. The raw materials having the composition shown in Table 1 were placed in a stainless steel container, a stirring rod and an air cooling tube were attached to the stainless steel container, and then nitrogen gas was passed through the side port. After the air in the stainless steel container was completely replaced with nitrogen, the contents were melted by heating with a heating bath. As the contents melt, start stirring, and while continuing to stir,
When the temperature reached 190°C, it was maintained at that temperature for 10 minutes and then cooled in a cooling bath to obtain a yellow solid. After melting the resulting yellow solid in 1000 g of dimethylformamide, intermediates (B ₁ ) to (B ₃ )
And for reference products (C ₁ ) and (C ₂ ), by adding a large excess of methyl alcohol,
For intermediate (B ₄ ), a precipitate was precipitated by adding a large excess of benzene. After washing the precipitate separated by filtering the contents with methyl alcohol, it was spread on a stainless steel pad and dried at 100°C for 60 minutes to obtain a yellow powder with the yield shown in Table 1. Intermediate (B ₁ ) ~
(B ₄ ) and reference products (C ₁ ) and (C ₂ ) were obtained. The weight average molecular weight of the intermediate (B ₁ ) etc. obtained as described above was determined using a DMF solvent and a separation column of Showa Denko AD813/S (8.0 mm x 250 mm,
The measurement was carried out using a gel permeation chromatograph (HLC-803D manufactured by Toyo Soda) equipped with two plates (6000 theoretical plates). The obtained molecular weight measurements are shown in the bottom column of Table 1. Here, the molar ratio (mol%) shown in Table 1 represents the proportion of each component when the total number of moles calculated from the weight and molecular weight of each component is 100.

[Table] Next, prepolymer (A) was synthesized and measured in a solution state using an inert solvent. That is, first, among the raw materials shown in Table 2,
Intermediates (B ₁ ), (B ₄ ) and dimethylacetamide were weighed into two four-necked flasks according to the proportions shown in Table 2, and a cooling tube and stirring rod were attached to the flask, and nitrogen gas was passed through the side port. . After the air in the flask was completely replaced with nitrogen, heating was performed using a heating bath. Stirring was performed at _the same time as heating, _and after confirming that the contents were completely dissolved, maleic acid N・N′-4・4-
Diphenylmethane-bis-imide was weighed in as shown in Table 2, and the prepolymer (A ₃ ),
( _A4 ) Maleic acid N.N'-4.4-diphenyl ether-bis-imide was weighed as shown in Table 2, the temperature was maintained at 80°C, and stirring was continued for 2 hours. Cooling was performed to obtain a prepolymer (A) solution. The weight average molecular weight was measured by gel permeation chromatography in the same manner as above, and the results are shown in the bottom column of Sheet 2. Separately, prepolymer (A) was synthesized in a high temperature molten state as follows. First, raw materials having the composition shown in the prepolymer (A ₅ ) column of Table 2 were weighed into a stainless steel container, a stirring rod and an air-cooled tube were attached, and nitrogen gas was flowed through the side port. After the air in the stainless steel container was completely replaced with nitrogen, heating was performed using a heating bath. Stirring was started as the contents melted, and stirring was continued for 20 minutes while maintaining the temperature at 170°C, followed by cooling in a cooling bath. After cooling, the contents were transferred to a mortar and pulverized to obtain prepolymer (A ₅ ) powder.

【table】 /
_CH3
Next, a method for preparing an example of the heat-resistant resin composition according to the first invention will be explained. The prepolymer synthesized earlier as follows
A heat-resistant resin composition of an example was prepared from the (A) solution and an epoxy resin. That is, solutions of prepolymers (A ₁ ) to (A ₄ ) synthesized in a solution state using an inert solvent were added to the phenol novolak type epoxy resin having the weight shown in Table 3. The indicated weights were blended to obtain heat-resistant resin composition solutions of Examples 1 to 4.

[Table] *1 Epicron manufactured by Dainippon Ink Co., Ltd. Next, a method for producing a prepreg, which is an embodiment of the second invention, and an example of obtaining a laminate using these prepregs will be described. As shown in Table 4, glass cloth (WE113, manufactured by Nittobo Co., Ltd.) whose surface had been previously treated with epoxy silane (300 mm x 300 mm) was impregnated with the heat-resistant resin composition solutions of Examples 1 to 4 previously obtained. These were heated to 150° C. and dried for 10 minutes to obtain four types of prepregs with a resin content of 48%, that is, prepregs of Examples 5 to 8. Using these prepregs of Examples 5 to 8, laminates were obtained in the following manner. The prepreg of Example 5 was used to form two types of laminates. Layer 4 sheets of the obtained prepreg, 300mm x 300mm
sandwiched between two plate molds, actual pressure 40Kg/cm ²
Primary heating was carried out under the conditions shown in Table 4, followed by secondary heating. Thereafter, after-curing was performed at 200°C for 120 minutes to obtain a dark red colored laminate. Table 4 also shows the glass transition temperatures of the molded bodies and laminates obtained above, as well as the measured values of the thermal decomposition onset temperatures when the temperature was raised at 5° C./min. Furthermore, as a comparative side, Table 4 also shows the measured values of the glass transition temperature and thermal decomposition onset temperature when the temperature was raised at 5° C./min for an epoxy laminate (Matsushita Electric Works product number R1661). From Table 4, the laminate obtained using the prepreg of the example of the second invention uses the heat-resistant resin composition of the first invention, so the glass transition temperature and thermal decomposition temperature are lower than those of the comparative example. It can be seen that it has high heat resistance.

[Table] Next, an embodiment of the third invention will be described. In this case, the previously mentioned prepolymer _A5 powder synthesized in a high temperature melt state is used. That is, the epoxy resin and each raw material were blended into this powder in the proportions shown in Table 5. This was heated and melted, kneaded, cooled and solidified, and then crushed to obtain a molding material.

【table】

〔Effect of the invention〕

As seen above, the heat-resistant resin composition according to the first invention allows an insulator with excellent heat resistance to be obtained. The prepreg according to the second invention and the molding material according to the third invention both use the heat-resistant resin composition according to the first invention as their resin composition, as described above. By using this method, it becomes possible to obtain highly heat-resistant laminates and molded bodies suitable for high-density packaging. As described above, the heat-resistant resin composition according to the first invention can be used as a varnish for laminated boards with excellent insulation properties and heat resistance, and as a molding material for electronic and electrical applications such as semiconductor packages, structural materials for electric appliances, and sliding materials. It is suitable for all applications for molded products such as.

Claims (1)

[Claims] 1. A prepreg formed by impregnating a base material with a resin composition, in which the resin composition is a compound having at least two epoxy groups in the molecule,
The following general formula () is added to the intermediate (B) obtained by reacting the maleimide compound represented by the following general formula () with the diamine represented by the following general formula () in advance.
1. A prepreg characterized by using a heat-resistant resin composition containing a prepolymer (A) obtained by reacting an unsaturated bis-imide represented by: (In the formula, R ₁ is a divalent organic group) H ₂ N−R ₂ −NH ₂ … () (In the formula, R ₂ is a divalent organic group) (In the formula, R ₃ is a divalent organic group) 2 Intermediate (B) is 50 to 90 mol% of a maleimide compound
The prepreg according to claim 1, which is obtained by reacting a diamine with 10 to 50 mol % of a diamine.