JP2010174062A - Heat resistant resin composition and molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat resistant resin composition without containing material adversely affecting environment, excellent in heat resistance, adhesiveness and curing property, and further having improved mechanical properties of the cured product; and a molded article obtained by using the same. <P>SOLUTION: The heat resistant resin composition includes (A)(a-1) an amionphenols having an amino group and a phenolic hydroxy group in one molecule, and (a-2) a predetermined bismaleimide compound; (B) an epoxy resin; (C) a silicone powder; and (D) a curing promoter as essential components. A molded article is obtained by using the composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention does not contain 4,4'-diaminodiphenylmethane, has little adverse effects on the environment, has good curing characteristics, and the cured product has high heat resistance, and has adhesiveness and mechanical characteristics. A heat-resistant resin composition that is good, for example, a heat-resistant resin composition that is suitable as a constituent material of a molding material, a grindstone, a brake, a dust core, and the like, and a molded article using the same

Conventionally, a heat-resistant resin composition has been obtained by a reaction between bismaleimide and an aromatic diamine (see, for example, Patent Document 1). Such a heat-resistant resin composition is generally used in a wide range of fields such as automobile parts, electronic / electrical parts, and mechanical parts because the cured product has good electrical and mechanical properties and heat resistance. Moreover, since such a heat resistant resin composition is excellent in slidability, it is also frequently used in the manufacture of mechanical parts.
However, heat resistance resin compositions are required to have higher heat resistance than conventional ones, and heat resistance resin compositions obtained by the reaction of bismaleimide and aromatic diamine as described above are also heat resistant. Improvement is required.

In addition, the heat resistant resin composition is also required to have little influence on the environment. For example, 4,4′-diaminodiphenylmethane (DDM) is used as a curing agent in the heat-resistant resin composition as described above. 4,4′-Diaminodiphenylmethane is a substance that has an adverse effect on the environment, and there are concerns about the impact on the environment and the human body not only during the production of the heat-resistant resin composition but also during the molding and use of the molded product. .
In order to solve such problems, it has been studied to use a compound having a similar amino group in place of 4,4′-diaminodiphenylmethane. However, when such a curing agent is used, there are problems such as a decrease in heat resistance as compared with that using 4,4′-diaminodiphenylmethane, and both environmental problems and maintenance and improvement of properties are compatible. I want to have a situation.
On the other hand, the present inventors have proposed a resin composition in which a specific polyimide is introduced in order to improve heat resistance without using 4,4′-diaminodiphenylmethane (see Patent Document 2).

Japanese Patent Publication No.46-23250 JP 2005-82628 A

  The heat-resistant resin composition is required not to use 4,4'-diaminodiphenylmethane or the like from the consideration of the environment. In particular, in applications such as brakes, clutches, dust cores, etc., it is required to have excellent heat resistance and excellent mechanical properties of the cured product, in particular, bending strength.

  The present invention has been made in view of the above-described situation, does not contain a substance that adversely affects the environment, is excellent in heat resistance, has excellent adhesiveness and curing characteristics, and is cured compared to conventional ones. An object of the present invention is to provide a heat-resistant resin composition in which the mechanical properties of the product are greatly improved and a molded product using the same.

  As a result of diligent study, the present inventors have (A) (a-1) aminophenols and (a-2) bismaleimide compounds, (B) epoxy resin, (C) silicone powder, and (D). It has been found that the above object can be achieved by a heat resistant resin composition containing a curing accelerator as an essential component, and the present invention has been completed.

That is, this invention provides the following heat resistant resin composition and a molded article using the same.
1. (A) (a-1) aminophenols having an amino group and a phenolic hydroxyl group in one molecule, and (a-2) a bismaleimide compound represented by the following chemical formula, (B) an epoxy resin, and (C) silicone powder And (D) a heat-resistant resin composition comprising a curing accelerator as an essential component.

[Wherein R ¹ represents a divalent group containing at least two carbon atoms. ]
2. (A) (a-1) A polyimide resin obtained by reacting an aminophenol having an amino group and a phenolic hydroxyl group in one molecule and (a-2) a bismaleimide compound represented by the following chemical formula, (B) A heat-resistant resin composition comprising an epoxy resin, (C) silicone powder, and (D) a curing accelerator as essential components.

[Wherein R ¹ represents a divalent group containing at least two carbon atoms. ]
3. Of the total amount of component (A), component (B), component (C) and component (D), the total amount of component (A) and component (B) is 90 to 99% by mass. 3. The heat resistant resin composition according to 1 or 2 above.
4). The heat resistant resin composition according to any one of the above items 1 to 3, wherein the component (A) is 50 to 95% by mass of the total amount of the component (A) and the component (B).
5). (C) The heat resistant resin composition according to any one of 1 to 4 above, wherein the particle shape of the component is spherical or substantially spherical.
6). (C) The specific gravity of a component is 0.95-1.5, and an average particle diameter is 1-40 micrometers, The heat resistant resin composition in any one of said 1-5 characterized by the above-mentioned.
7). (A) (a-1) aminophenols having an amino group and a phenolic hydroxyl group in one molecule and (a-2) a bismaleimide compound represented by the following chemical formula, or the component (a-1) and (a -2) Mixing (C) silicone powder with a pulverized product of a heat-melt mixture containing a polyimide resin obtained by reacting the component, (B) an epoxy resin, and (D) a curing accelerator. 7. The heat-resistant resin composition according to any one of 1 to 6 above.

[Wherein R ¹ represents a divalent group containing at least two carbon atoms. ]
8). A molded article obtained by molding the heat-resistant resin composition according to any one of 1 to 7 above.

  The present invention uses aminophenols and bismaleimide compounds, or polyimide resins, epoxy resins, silicone powders, and curing accelerators obtained by reacting them as essential components, so that there are very few adverse effects on the environment and heat resistance. In addition to excellent properties, it is possible to provide a heat-resistant resin composition excellent in adhesive properties and curing properties, and in particular improved in mechanical properties such as bending strength of the cured product, and a molded article using the same.

[Heat resistant resin composition]
The heat resistant resin composition of the present invention comprises (A) (a-1) aminophenols having an amino group and a phenolic hydroxyl group in one molecule (hereinafter simply referred to as (a-1) aminophenols) and (A-2) A bismaleimide compound represented by the following chemical formula (hereinafter simply referred to as (a-2) bismaleimide compound), (B) an epoxy resin, (C) silicone powder, and (D) a curing accelerator are essential. Ingredients.

In the above chemical formula, R ¹ represents a divalent group containing at least two carbon atoms.
The components (A) to (D) will be described below.

(A) (a-1) Aminophenols and (a-2) Bismaleimide Compound Among the components (A) in the heat resistant resin composition of the present invention, (a-1) aminophenols serve as a curing agent. It is mainly added to cure (a-2) bismaleimide compound and (B) epoxy resin.
Even if the component (A) in the heat resistant resin composition of the present invention is in a state where (a-1) aminophenols and (a-2) bismaleimide compound are not reacted, (a-1) aminophenols And (a-2) a polyimide resin obtained by reacting a bismaleimide compound.

(A-1) Aminophenols have a primary amino group and a phenolic hydroxyl group in one molecule, such as orthoaminophenol, metaaminophenol, paraaminophenol, 4-amino-4′-hydroxy. Examples include phenylpropane, 2-amino-4-chlorophenol and 2-amino-4-cresol. These may be used individually by 1 type and may be used in combination of 2 or more type.
(A-2) The bismaleimide compound is represented by the following chemical formula.

In the above chemical formula, R ¹ represents a divalent group containing at least two carbon atoms.
(A-2) As the bismaleimide compound, for example, N, N′-3,3′-diphenylmethane bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-3,3′- Diphenyl ether bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-paraphenylene bismaleimide, N, N′-metaphenylene bismaleimide, N, N ′-(2-methylmetaphenylene) Examples thereof include bismaleimide, N, N ′-(3,3′-dimethyldiphenylmethane) bismaleimide and N, N ′-(3,3′-diphenylsulfone) bismaleimide. These may be used individually by 1 type and may be used in combination of 2 or more type.

(B) Epoxy Resin The (B) epoxy resin in the heat resistant resin composition of the present invention is mainly added to improve the adhesiveness of the heat resistant resin composition. (B) The epoxy resin is not particularly limited, and generally known epoxy resins can be widely used.

  (B) As the epoxy resin, for example, an epoxy resin obtained by epoxidizing a condensate of phenol or alkylphenols and hydroxybenzaldehyde, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a naphthol novolak type epoxy resin, Examples thereof include bisphenol A novolac epoxy resin, bisphenol A glycidyl ether, epoxidized tetra (hydroxyphenyl) alkane, and bishydroxybiphenyl epoxy resin.

  (B) The epoxy resin is preferably a solid epoxy resin having a molecular weight of 1000 to 3000 in order to obtain good reactivity and moldability. As such a thing, Epicoat 1000 series (Japan Epoxy Resin Co., Ltd. make, brand name) etc. of a bisphenol A type epoxy resin etc. are mentioned, for example. This (B) epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) Silicone powder (C) Silicone powder in the heat-resistant resin composition of the present invention is, for example, a powder obtained by blending silicone oil with an inorganic carrier, and a silicone resin obtained by three-dimensionally crosslinking silicone oil. Those obtained by pulverization or those obtained by pulverizing silicone rubber can be used.
(C) The particle shape of the silicone powder is preferably spherical or substantially spherical in that it is difficult to aggregate. Moreover, it is preferable that the specific gravity of (C) silicone powder is 0.95-1.5, and an average particle diameter is 1-40 micrometers.
Examples of the (C) silicone powder include Trefil F series, Trefil E series (both manufactured by Toray Dow Corning Silicone Co., Ltd., trade name), KMP-590 series (made by Shin-Etsu Chemical Co., Ltd., trade name), etc. Is mentioned. This (C) silicone powder may be used individually by 1 type, and may be used in combination of 2 or more type.

(D) Curing accelerator (D) The curing accelerator in the heat resistant resin composition of the present invention is added to impart rapid curability to the heat resistant resin composition.
(D) The curing accelerator is not particularly limited as long as it is generally used for curing a thermosetting resin composition. For example, trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine. , Tri (p-methylphenyl) phosphine, tri (nonylphenylphosphine), methyldiphenylphosphine, dibutylphenylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane and bis (diphenylphosphino) methane Organic phosphine compounds; 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole Imidazole compounds or derivatives thereof; DBU (1,8-diazabicyclo [5,4,0] Undensen -7) or a phenol salt. These may be used individually by 1 type and may be used in combination of 2 or more type.

(Content)
The content of (a-1) aminophenols and (a-2) bismaleimide compound in component (A) is the total amount of (a-1) aminophenols and (a-2) bismaleimide compound. Among them, the content of (a-1) aminophenols is preferably 5 to 20% by mass.
When component (A) is a polyimide resin obtained by reaction of (a-1) aminophenols with (a-2) bismaleimide compound, (a-1) aminophenols used in the reaction and (a- 2) Of the total amount with the bismaleimide compound, the amount used for the reaction of (a-1) aminophenols is preferably 5 to 20% by mass.

(A-1) It is preferable that the aminophenols are 5% by mass or more because the curing characteristics are good without lowering the reactivity. Moreover, if (a-1) aminophenols are 20 mass% or less, since a viscosity will not become high too much and a moldability will become favorable, it is preferable, (a-2) Content of a bismaleimide compound also decreases. However, it is preferable because the heat resistance is good.
(A-1) Aminophenols and (a-2) bismaleimide compounds are the ratio of the number of amino groups in (a-1) aminophenols and the number of unsaturated bonds in (a-2) bismaleimide compounds [= (A-1) The number of amino groups of aminophenols / (a-2) the number of unsaturated bonds of bismaleimide compound] is more preferably adjusted so that the amount thereof is 0.1 to 0.5. If this ratio is 0.1 or more, the curing reaction proceeds sufficiently, and if it is 0.5 or less, the physical properties of the cured product, particularly heat resistance, is preferred without being lowered.

Moreover, it is preferable that (A) component is 50-95 mass% among the total amount of (A) component and (B) component. If the content of the component (A) is 50% by mass or more, the heat resistance of the cured product is preferably not lowered. .
Furthermore, out of the total amount of the component (A), the component (B), the component (C) and the component (D), the total amount of the component (A) and the component (B) is 90 to 99% by mass. preferable. If the total content of the component (A) and the component (B) is 90% by mass or more, curability, moldability, adhesiveness, etc. are good, and if it is 99% by mass or less, the adhesiveness is lowered. This is preferable. More preferably, the total content of the component (A) and the component (B) is 95 to 99% by mass.

(Optional component)
In addition to the above components (A) to (D), the heat-resistant resin composition of the present invention is not limited to the object of the present invention, but also a thermosetting resin, a thermoplastic resin, a release agent, a colorant, and a coupling. Agents, particulate or fibrous organic or inorganic fillers and the like may be added.
As other thermosetting resins, for example, polyamideimide having high heat resistance, etc., as release agents, synthetic wax, natural wax, esters, metal salts of linear fatty acids, acid amides, paraffins, etc., as coloring agents Includes carbon black.
In addition, particulate or fibrous organic or inorganic filler is added to improve the mechanical properties of the cured product, for example, organic filler such as tetrafluoroethylene polymer, silica, mica, metal oxide, Examples include inorganic fillers such as diamond, graphite and carbon.

[Method for producing heat-resistant resin composition]
The heat resistant resin composition of the present invention may be, for example, a state where the components (A) to (D) are simply mixed, or the components (A) to (D) are heated at a temperature at which they are not completely crosslinked. Alternatively, it may be in a state of being heat-kneaded.
Furthermore, the heating or heating kneading is not necessarily performed for all the components (A) to (D). For example, heating or heating kneading is performed on the components (A), (B), and (D). The component (C) may be simply added to the mixture and mixed.

That is, the heat resistant resin composition of the present invention can be produced, for example, as follows.
(A) (a-1) Aminophenol powder having an average particle diameter of 2 to 200 μm, (a-2) Bismaleimide compound having an average particle diameter of 2 to 200 μm, (B) Epoxy resin having an average particle diameter of 2 to 2 200 μm powder, (C) silicone powder having an average particle diameter of 1 to 40 μm, and (D) a curing accelerator are prepared, and these are uniformly mixed at about 100 to 150 ° C., and heated roll or kneader. A heat-melting / mixing treatment is performed, followed by cooling and solidification, and pulverization to an appropriate size to obtain a heat resistant resin composition.
In such a method, (C) silicone powder is not necessarily added from the beginning. For example, (A) (a-1) a powder of aminophenols having an average particle diameter of 2 to 200 μm, (a-2) bis A maleimide compound having an average particle diameter of 2 to 200 μm, (B) an epoxy resin having an average particle diameter of 2 to 200 μm, and (D) a curing accelerator are uniformly mixed at about 100 to 150 ° C. Heat melting and mixing with a kneader or the like, followed by cooling and solidification, pulverization to an appropriate size to obtain a pulverized product, and (C) silicone powder may be simply added to the pulverized product and mixed.

Moreover, you may manufacture by the solution mixing method as another manufacturing method. For example, (A) (a-1) aminophenols and (a-2) bismaleimide compound, (B) epoxy resin, (C) silicone powder, and (D) curing accelerator are added to an organic polar solvent. 0 to 120 ° C., preferably 0 to 100 ° C., and then uniformly dissolved, and then precipitated in a poor solvent such as water, methanol or ethanol, the precipitate is dried, and the precipitate is pulverized as necessary. The powder of the heat resistant resin composition having an average particle diameter of 1 to 150 μm, preferably 10 to 30 μm can be obtained by pulverization.
Also in the solution mixing method, (C) silicone powder does not necessarily need to be added to the organic polar solvent from the beginning. For example, (A) (a-1) aminophenols, (a-2) bismaleimide compound, ( B) An epoxy resin and (D) a curing accelerator are added to an organic polar solvent and uniformly dissolved at 0 to 120 ° C., preferably 0 to 100 ° C., and then in a poor solvent such as water, methanol or ethanol. The precipitate is dried, and (C) silicone powder is added thereto, mixed, and, if necessary, the precipitate is pulverized and powdered to obtain an average particle size of 1 to 150 μm, preferably 10 It is also possible to obtain a powder of a heat-resistant resin composition of ˜30 μm.

In the above production method of the present invention, the method in which (C) the silicone powder is added after being added is preferable because the bending property of the molded product is increased.
Moreover, in the said manufacturing method, the arbitrary component mentioned above other than (A)-(D) component can be selected suitably as needed, and can be added.
In the above production method, as described above, as component (A), instead of (a-1) aminophenols and (a-2) bismaleimide compounds, (a-1) aminophenols and (a-2) ) A polyimide resin obtained by reacting with a bismaleimide compound may be used.

[Molding]
The heat-resistant resin composition of the present invention produced by the production method described above can be used for producing a molded product using a molding method such as low-pressure transfer, injection molding, compression molding or the like. Further, the molding can be performed at a molding temperature of about 200 to 230 ° C.
Since the heat-resistant resin composition of the present invention does not contain 4,4′-diaminodiphenylmethane and the like, there are few adverse effects on the environment, it has excellent curing characteristics, and is excellent in the characteristics of the cured product, particularly heat resistance. It can be suitably used as a constituent material for various parts in the electric and electronic fields such as grinding wheels, brakes, dust cores, and automobiles.

The examples illustrate the invention. In addition, this invention is not limited by these Examples.
The heat resistant resin composition was manufactured by the composition of Examples 1-6 and Comparative Examples 1-4 shown below. In addition, Examples 1-3 and Comparative Examples 1-4 were manufactured by the manufacturing method 1, and Examples 4-6 were manufactured by the manufacturing method 2.

[Example 1]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 69.07 mass%, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals) 8.6 mass% , (B) bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.) 6.9% by mass, bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.4% by mass, (C) Silicone powder AY49-518 (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) 5% by mass, (D) Curing accelerator 2-methylimidazole 0.03% by mass.

[Example 2]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 70.47% by mass, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals) 8.7% by mass (B) 7.1% by mass of bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.7% by mass, (C) silicone powder AY49-518 (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) 3% by mass, (D) curing accelerator 2-methylimidazole 0.03% by mass.

[Example 3]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 71.97% by mass, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals, Inc.) 8.9% by mass , (B) bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.) 7.2 mass%, bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.9% by mass, (C) silicone powder AY49-518 (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) 1% by mass, (D) curing accelerator 2-methylimidazole 0.03% by mass.

[Example 4]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 69.07 mass%, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals) 8.6 mass% , (B) bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.) 6.9% by mass, bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.4% by mass, (C) Silicone powder AY49-518 (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) 5% by mass, (D) Curing accelerator 2-methylimidazole 0.03% by mass.

[Example 5]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 70.47% by mass, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals) 8.7% by mass (B) 7.1% by mass of bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.7% by mass, (C) silicone powder AY49-518 (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) 3% by mass, (D) curing accelerator 2-methylimidazole 0.03% by mass.

[Example 6]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 71.97% by mass, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals, Inc.) 8.9% by mass , (B) bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.) 7.2 mass%, bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.9% by mass, (C) silicone powder AY49-518 (trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) 1% by mass, (D) curing accelerator 2-methylimidazole 0.03% by mass.

[Comparative Example 1]
(A) (a-1) metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 72.67 mass%, (a-2) bismaleimide-S (trade name, manufactured by Mitsui Chemicals) 9 mass%, ( B) Bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.) 7.3 mass%, Bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.), 11 mass %, (D) Curing accelerator 2-methylimidazole 0.03 mass%.

[Comparative Example 2]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 70.47% by mass, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals) 8.7% by mass (B) 7.1% by mass of bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.7% by mass, calcined polytetrafluoroethylene resin powder KT-400M (trade name, manufactured by Kitamura Co., Ltd.) 3% by mass, (D) curing accelerator 2-methylimidazole 0.03% by mass.

[Comparative Example 3]
(A) (a-1) Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 70.47% by mass, (a-2) Bismaleimide-S (trade name, manufactured by Mitsui Chemicals) 8.7% by mass (B) 7.1% by mass of bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.7% by mass, organically modified silicone oil Silaace S-501 (trade name, manufactured by Chisso Corporation) 3% by mass, (D) curing accelerator 2-methylimidazole 0.03% by mass.

[Comparative Example 4]
(A) (a-1) metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 72.47% by mass, (a-2) bismaleimide-S (product name, manufactured by Mitsui Chemicals) 8.9% by mass (B) Bisphenol A type epoxy resin 1004 (trade name, molecular weight of about 1650, manufactured by Japan Epoxy Resin Co., Ltd.) 7.29% by mass, Bisphenol A type epoxy resin 1007 (trade name, molecular weight of about 2900, manufactured by Japan Epoxy Resin Co., Ltd.) 10.9 mass%, organic vulcanizing agent Actor R (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.) 0.3 mass%, (D) curing accelerator 2-methylimidazole 0.03% by mass.

[Production Method 1]
By heating kneader, (A) (a-1) aminophenols, (a-2) bismaleimide compound, (B) epoxy resin, (C) silicone powder or calcined polytetrafluoroethylene resin powder, silicone oil or vulcanization The agent and (D) curing accelerator were heated, melted and mixed at 130 ° C., then cooled and solidified, and pulverized to a predetermined size to obtain a heat resistant resin composition.

[Production Method 2]
First, (A) (a-1) aminophenols, (a-2) bismaleimide compound and (D) curing accelerator were heated, melted and mixed at 130 ° C. by heating kneader, and (B) epoxy resin was added. The mixture was heated, melted and mixed at 130 ° C., cooled and solidified, and pulverized to a predetermined size. Further, fine powder of (C) silicone powder was added to this pulverized product, and mixed to obtain a heat resistant resin composition.

[Evaluation methods]
Next, with respect to the heat resistant resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4, the gel time, the bending strength, and the specific resistance were measured, and the cured products were evaluated for heat resistance by 5% mass reduction temperature. Were measured and evaluated. The measurement method is as follows, and the results are shown in Table 1.
(Measurement of gel time)
When a certain amount of heat-resistant resin composition in a hot plate shape maintained at 200 ° C. is spread on a circle with a diameter of 4 to 5 cm and kneaded at a constant speed, the heat-resistant resin composition thickens and eventually becomes viscous. The time lost was measured.
(Measurement of bending strength and specific resistance)
A mixture of a heat-resistant resin composition and iron powder (average particle size of about 1 μm) as a filler in a ratio of 0.2: 99.8 is molded into a size of 60 mm × 10 mm × 5 mm (pressure 800 N / mm ² ) and the molded article was fired in air at a temperature of 350 ° C. for 30 minutes to prepare a test piece. Using this test piece, the bending strength was measured according to JISK6911, and the specific resistance was measured by the four-terminal method.
(Heat-resistant)
The 5% mass reduction temperature was TG-DTA (manufactured by Seiko Instruments Inc.), and the temperature at which the mass reduction of the test piece produced in the same manner as described above was 5% was measured at a heating rate of 10 ° C./min.

  From Table 1, it can be seen that the heat resistance resin compositions of the examples have improved bending strength without impairing the adhesiveness, heat resistance, and electrical characteristics as compared with the heat resistance resin compositions of the comparative examples.

  Since the heat-resistant resin composition of the present invention does not contain 4,4′-diaminodiphenylmethane or the like, it has little adverse effect on the environment, has good curing characteristics, and the cured product has high heat resistance. Further, since the adhesiveness and mechanical properties are also good, it is suitable as a constituent material for molding materials, grindstones, brakes, dust cores and the like.

Claims (8)

(A) (a-1) aminophenols having an amino group and a phenolic hydroxyl group in one molecule, and (a-2) a bismaleimide compound represented by the following chemical formula, (B) an epoxy resin, and (C) silicone powder And (D) a heat-resistant resin composition comprising a curing accelerator as an essential component.

[Wherein R ¹ represents a divalent group containing at least two carbon atoms. ] (A) (a-1) A polyimide resin obtained by reacting an aminophenol having an amino group and a phenolic hydroxyl group in one molecule and (a-2) a bismaleimide compound represented by the following chemical formula, (B) A heat-resistant resin composition comprising an epoxy resin, (C) silicone powder, and (D) a curing accelerator as essential components.

[Wherein R ¹ represents a divalent group containing at least two carbon atoms. ]   Of the total amount of component (A), component (B), component (C) and component (D), the total amount of component (A) and component (B) is 90 to 99% by mass. The heat-resistant resin composition according to claim 1 or 2.   4. The heat resistant resin composition according to claim 1, wherein the component (A) is 50 to 95% by mass in the total amount of the component (A) and the component (B). object.   The heat resistant resin composition according to any one of claims 1 to 4, wherein the particle shape of the component (C) is spherical or substantially spherical.   The specific gravity of (C) component is 0.95-1.5, and an average particle diameter is 1-40 micrometers, The heat resistant resin composition of any one of Claims 1-5 characterized by the above-mentioned. . (A) (a-1) aminophenols having an amino group and a phenolic hydroxyl group in one molecule and (a-2) a bismaleimide compound represented by the following chemical formula, or the component (a-1) and (a -2) Mixing (C) silicone powder with a pulverized product of a heat-melt mixture containing a polyimide resin obtained by reacting the component, (B) an epoxy resin, and (D) a curing accelerator. The heat-resistant resin composition according to any one of claims 1 to 6.

[Wherein R ¹ represents a divalent group containing at least two carbon atoms. ]   A molded article obtained by molding the heat-resistant resin composition according to any one of claims 1 to 7.