JP2005082626A - Heat-resistant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-resistant resin composition which does not contain 4,4-diaminodiphenylmethane affecting environments as a curing agent, has excellent curing characteristics, and gives a cured product having excellent mechanical characteristics and heat resistance. <P>SOLUTION: This heat-resistant resin composition is characterized by containing (A) an aminophenol compound having an amino group and a phenolic hydroxy group in the molecule and (B) a bisallylnadimide type polyimide resin represented by chemical formula (1) (R is a divalent group having at least two carbon atoms) as essential components. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a heat-resistant resin composition that does not contain 4,4-diaminodiphenylmethane, has little adverse effects on the environment, has excellent curing characteristics, and has excellent heat resistance and mechanical characteristics of cured products. The present invention relates to a heat resistant resin composition suitable as a constituent material for laminates, grindstones, brakes and the like.

  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 used in a wide range of fields such as automobile parts, electronic / electrical parts, and mechanical parts because the cured product is excellent in electrical, mechanical characteristics, 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, the heat resistant resin composition is required not only to have excellent electrical and mechanical properties and heat resistance, but also 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 influence 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 amine 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.
Shoko 46-23250

  The heat-resistant resin composition is required not to use 4,4'-diaminodiphenylmethane or the like in consideration of the environment. Further, the heat resistant resin composition is required to be excellent in curing characteristics and excellent in electrical, mechanical characteristics and heat resistance of the cured product.

  The present invention has been made to solve the above-described problems, does not contain a substance that adversely affects the environment, has excellent curing characteristics, and has excellent mechanical properties and heat resistance of cured products. The object is to provide a resin composition.

（但し、式中、Ｒは少なくとも２個の炭素原子を含む２価の基を示す。）
を必須成分としてなることを特徴とする。 The heat-resistant resin composition of the present invention comprises: (A) an aminophenol having an amino group and a phenolic hydroxyl group in one molecule; and (B) a bisallylnadiimide-type polyimide resin represented by the following chemical formula (1):

(In the formula, R represents a divalent group containing at least 2 carbon atoms.)
Is an essential component.

  Of the (A) aminophenol having an amino group and a phenolic hydroxyl group in one molecule and (B) a total amount of 100% by weight of the bisallylnadiimide-type polyimide resin represented by the chemical formula (1), (A ) The content of aminophenols having an amino group and a phenolic hydroxyl group in one molecule is preferably 5 to 20% by weight.

（但し、式中、Ｒは少なくとも２個の炭素原子を含む２価の基を示す。）
（Ｃ）エポキシ樹脂とを必須成分としてなることを特徴とする。 Another heat-resistant resin composition of the present invention comprises (A) an aminophenol having an amino group and a phenolic hydroxyl group in one molecule, and (B) a bisallyl nadiimide type represented by the following chemical formula (1). Polyimide resin,

(In the formula, R represents a divalent group containing at least 2 carbon atoms.)
(C) An epoxy resin is an essential component.

  (A) Aminophenol having an amino group and a phenolic hydroxyl group in one molecule, (B) a bisallylnadiimide type polyimide resin represented by chemical formula (1) and (C) an epoxy resin in a total amount of 100% by weight Among them, (A) the content of aminophenols having an amino group and a phenolic hydroxyl group in one molecule is 5 to 20% by weight, and the content of the (C) epoxy resin is 5 to 20% by weight. It is preferable.

  In the present invention, specific aminophenols and bisallylnadiimide type polyimide resins are used as essential components, so that there are very few adverse effects on the environment, excellent curing properties, and mechanical properties and heat resistance of cured products. It becomes possible to provide an excellent heat resistant resin composition.

  Moreover, in this invention, it becomes possible to make a heat resistant resin composition excellent in adhesiveness by adding an epoxy resin other than the said specific aminophenol and bisallyl nadiimide type polyimide resin.

Embodiments of the present invention will be described below.
The heat-resistant resin composition of the present invention is characterized in that (A) an aminophenol having an amino group and a phenolic hydroxyl group in one molecule and (B) a bisallylnadiimide type polyimide resin are essential components. .

  The (A) aminophenols used in the present invention are added to cure the (B) bisallylnadiimide type polyimide resin.

  The (A) aminophenol used in the present invention has a primary amino group and a phenolic hydroxyl group in one molecule. Specifically, orthoaminophenol, metaaminophenol, paraaminophenol, 4- Amino-4'-hydroxyphenylpropane, 2-amino-4-chlorophenol, 2-amino-4-cresol and the like can be mentioned.

（但し、式中、Ｒは少なくとも２個の炭素原子を含む２価の基を示す。） The (B) bisallyl nadiimide type polyimide resin used in the present invention is represented by the following chemical formula (1).

(In the formula, R represents a divalent group containing at least 2 carbon atoms.)

(B) Bisallyl nadiimide type polyimide resin is more preferable if R part in the said Chemical formula (1) is shown by following Chemical formula (2)-(4).

  As the R moiety in the chemical formula (1) represented by the chemical formulas (2) to (4), commercially available ones can be used. For example, R in the chemical formula (1) can be used. BANI-M (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) when the portion is the chemical formula (2), and BANI-H (Maruzen Petrochemical Co., Ltd.) when the R portion of the chemical formula (1) is the chemical formula (3). Product name), and BANI-X (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) in the case where the R portion of the chemical formula (1) is the chemical formula (4).

  The heat resistant resin composition of the present invention may be composed of (A) aminophenols having an amino group and a phenolic hydroxyl group in one molecule and (B) bisallylnadiimide type polyimide resin. In addition, (C) an epoxy resin may be added.

  (C) The epoxy resin shortens the curing time of the heat-resistant resin composition or improves the adhesion between the heat-resistant resin composition and the metal part when the metal part is embedded in the heat-resistant resin composition and molded. Therefore, any epoxy resin having two or more epoxy groups in one molecule can be used without particular limitation.

  Specifically, the epoxy resin (C) is preferably used by appropriately selecting from monomers having an epoxy group and the whole polymer in consideration of gel time characteristics, softening point, etc., for example, o-cresol novolac type epoxy resin, biphenyl type Epoxy resins, dicyclopentadiene-based epoxy resins, and other generally known epoxy resins can be used.

  In the heat resistant resin composition of the present invention, when (C) an epoxy resin is not included, (A) aminophenols and (B) bisallylnadiimide type polyimide resin in a total amount of 100% by weight (A ) The content of aminophenols is preferably 5 to 20% by weight.

  (A) Reactivity will fall that content of aminophenols is less than 5 weight%, and hardening characteristics will fall. If it exceeds 20% by weight, the viscosity will increase and the moldability will be inferior.

  When the heat resistant resin composition of the present invention contains (C) an epoxy resin, the total amount of (A) aminophenols, (B) bisallylnadiimide type polyimide resin, and (C) epoxy resin is 100 weights. %, The content of (A) aminophenols is preferably 5 to 20% by weight, and the content of (C) epoxy resin is preferably 5 to 20% by weight.

  (A) Reactivity will fall that content of aminophenols is less than 5 weight%, and hardening characteristics will fall. If it exceeds 20% by weight, the viscosity increases and the moldability is inferior, which is not preferable, and the mechanical properties, heat resistance and the like of the cured product are also deteriorated, which is not preferable.

  In addition, when the content of (C) the epoxy resin is less than 5% by weight, the effect of shortening the curing time of the heat-resistant resin composition or improving the adhesiveness of the heat-resistant resin composition is low. Exceeding this is not preferable because the mechanical properties, heat resistance, etc. of the cured product are lowered.

  Furthermore, regardless of the presence or absence of (C) epoxy resin, the content of (A) aminophenols and (B) bisallylnadiimide type polyimide resin is such that the number of amino groups in (A) aminophenols and (B) The ratio of the number of unsaturated bonds of the lunadiimide type polyimide resin (= (A) number of amino groups of aminophenols / (B) number of unsaturated bonds of bisallylnadiimide type polyimide resin) is 0.1 to 0.5. It is more preferable that it is adjusted so as to be.

  If the ratio is less than 0.1, the curing reaction is not likely to occur sufficiently, and if the ratio exceeds 0.5, the characteristics of the cured product, particularly heat resistance, is deteriorated.

  The heat resistant resin composition of the present invention comprises (A) an aminophenol and (B) a bisallylnadiimide type polyimide resin, or (A) an aminophenol and (B) a bisallylnadiimide type polyimide resin, and (C) Although it is good also as what consists of an epoxy resin, in order to provide rapid curability to a heat resistant resin composition, it is preferable to contain a hardening accelerator in addition to these things.

  The curing accelerator is not particularly limited as long as it is generally used for curing the thermosetting resin composition. For example, trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tri ( Organic phosphine compounds such as p-methylphenyl) phosphine, tri (norylphenylphosphine), methyldiphenylphosphine, dibutylphenylphosphine, tricyclohexylphosphine, 1,2-bis (diphenylphosphino) ethane, bis (diphenylphosphino) methane , 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Or a derivative thereof, DBU (1,8-diazabicyclo (5,4,0) undencene-7) or a phenol salt thereof, etc., which may be used alone or in combination of two or more. You may mix and use.

  The addition amount of the curing accelerator cannot be generally determined because the catalyst activity of each curing accelerator is different. However, (A) aminophenols, (B) bisallylnadiimide type polyimide resin and (C ) When the total amount of epoxy resin is 100 parts by weight, it is preferably added in the range of 0.1 to 5 parts by weight. If the amount is less than 0.1 parts by weight, improvement of the curing characteristics cannot be expected, and if it exceeds 5 parts by weight, the fluidity and manufacturability are lowered, and the heat resistance of the cured product is also lowered.

  Further, in the heat-resistant resin composition of the present invention, other thermosetting resins, thermoplastic resins, particulate or fibrous organic or inorganic fillers, mold release agents, colorants as long as they do not contradict the purpose of the present invention. A coupling agent or the like may be added.

  In the present invention, the mechanical properties of the cured product can be improved by containing a particulate or fibrous organic or inorganic filler. Examples of the filler include organic fillers such as wood powder and pulp, and inorganic fillers such as calcium carbonate, clay and talc.

  When the heat-resistant resin composition of the present invention contains a particulate or fibrous organic or inorganic filler, the total of (A) aminophenols, (B) bisallylnadiimide type polyimide resin, and (C) epoxy resin It is more preferable to add 100 parts by weight or more with respect to 100 parts by weight. By adding 100 parts by weight or more of a particulate or fibrous organic or inorganic filler, the curing characteristics of the heat resistant resin composition can be improved, and the moldability can be further improved.

  Since the heat-resistant resin composition of the present invention as described above does not contain 4,4-diaminodiphenylmethane or the like, there are few adverse effects on the environment, and it has excellent curing characteristics and excellent heat resistance and mechanical characteristics of the cured product. For example, it can be suitably used as a constituent material for various parts in the electric and electronic fields such as molding materials, laminated plates, grindstones, and brakes, and in the automotive field.

Next, the manufacturing method of the heat resistant resin composition of this invention is demonstrated.
For example, (A) a fine powder having an average particle size of about 2 to 200 μm is prepared as an aminophenol having an amino group and a phenolic hydroxyl group in one molecule, and (B) a bisallylna compound represented by the chemical formula (1). A fine powder having an average particle diameter of about 2 to 200 μm is prepared as a diimide type polyimide resin. A predetermined amount of these powders are uniformly mixed at a temperature of about 100 to 150 ° C., heated and mixed with a hot roll or kneader, then cooled and solidified, and pulverized to an appropriate size to obtain a heat resistant resin composition. To do.

  In addition to the methods described above, the heat resistant resin composition can be produced by a solution mixing method. That is, (A) aminophenols having an amino group and a phenolic hydroxyl group in one molecule and (B) a bisallylnadiimide type polyimide resin represented by the chemical formula (1) are added to an organic polar solvent in predetermined amounts. 0-120 ° C., preferably 0-100 ° C., and then uniformly dissolved, then precipitated in a poor solvent such as water, methanol or ethanol, the precipitate is dried, and the precipitate is crushed as necessary The powder of the heat resistant resin composition having an average particle diameter of 1 to 150 μm, more preferably 10 to 30 μm may be obtained by pulverization.

  Next, an example explains the present invention. In addition, this invention is not limited by these Examples.

(Example 1)
Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 15% by weight, 85% by weight of bisallyldiimide type polyimide resin BANI-M (melting point 75 ° C.) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) Then, a heat-melt mixing process was performed with a hot roll, then cooled and solidified, and pulverized to a predetermined size to obtain a heat-resistant resin composition.

(Example 2)
15% by weight of metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.), 85% by weight of bisallyldiimide type polyimide resin BANI-X (melting point: 40 ° C.) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) Then, a heat-melt mixing process was performed with a hot roll, then cooled and solidified, and pulverized to a predetermined size to obtain a heat-resistant resin composition.

(Comparative Example 1)
4,4-diaminodiphenylmethane (DDM) 15% by weight, bismaleimide resin (melting point 145 ° C.) (trade name, manufactured by Mitsui Chemicals, Inc.) 85% by weight are uniformly mixed, and heated and mixed with a hot roll. Subsequently, the mixture was cooled and solidified, and pulverized to a predetermined size to obtain a heat resistant resin composition.

(Comparative Example 2)
4,4-diaminodiphenylmethane (DDM) 10% by weight, bismaleimide resin (melting point 145 ° C.) (trade name, manufactured by Mitsui Chemicals, Inc.) 90% by weight are uniformly mixed, and heated and mixed with a hot roll. Subsequently, the mixture was cooled and solidified, and pulverized to a predetermined size to obtain a heat resistant resin composition.

  For these heat-resistant resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2, gel time and moldability (viscosity) were measured, and heat resistance (5% weight loss temperature) and mechanical properties of those cured products ( Flexural strength) and free DDM were measured. The results are shown in Table 1.

  In addition, when the gel time is spread on a hot plate kept at 200 ° C., a certain amount of the heat-resistant resin composition is formed into a circle having a diameter of 4 to 5 cm, and kneaded at a constant speed, the heat-resistant resin composition increases in viscosity. The time when the stickiness disappeared was measured. The viscosity was measured at 150 ° C. using a HaKKe rotational viscometer.

  As the 5% weight loss temperature, TG-DTA (manufactured by Seiko Instruments Inc.) was used, and the temperature at which the weight loss was 5% was measured at a heating rate of 20 ° C./min. The bending strength was measured based on JISK6911, and the free DDM was measured using gas chromatography.

  As is clear from Table 1, the heat-resistant resin compositions of the examples do not release 4,4-diaminodiphenylmethane unlike the heat-resistant resin compositions of the comparative examples, and the heat-resistant resin compositions of the comparative examples. It was found to have the same moldability, mechanical properties and heat resistance as

(Example 3)
Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 9.8% by weight, bisallylnadiimide type polyimide resin BANI-M (melting point 75 ° C.) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) 75% by weight, bisphenol A Type epoxy resin 1004 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) 15% by weight and curing accelerator 2-methylimidazole 0.2% by weight are uniformly mixed, heated and mixed with a hot roll, and then cooled and solidified. And pulverized to a predetermined size to obtain a heat-resistant resin composition.

Example 4
Metaaminophenol (trade name, manufactured by Sumitomo Chemical Co., Ltd.) 9.8% by weight, bisallylnadiimide type polyimide resin BANI-X (melting point 40 ° C.) (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) 75% by weight, bisphenol A Type epoxy resin 1004 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) 15% by weight and curing accelerator 2-methylimidazole 0.2% by weight are uniformly mixed, heated and mixed with a hot roll, and then cooled and solidified. And pulverized to a predetermined size to obtain a heat-resistant resin composition.

(Comparative Example 3)
4,4-diaminodiphenylmethane (DDM) 9.8% by weight, bismaleimide resin (melting point 145 ° C.) (trade name, manufactured by Mitsui Chemicals) 75% by weight, bisphenol A type epoxy resin 1004 (product manufactured by Japan Epoxy Resin Co., Ltd.) Name) 15% by weight and 0.2% by weight of curing accelerator 2-methylimidazole are uniformly mixed, heated and mixed with a hot roll, then solidified by cooling, pulverized to a predetermined size, and heat-resistant resin A composition was obtained.

  For these heat-resistant resin compositions of Examples 3 and 4 and Comparative Example 3, gel time and moldability (viscosity) were measured, and adhesiveness (aluminum plate adhesion test) and heat resistance (5% weight loss) of those cured products. Temperature), mechanical properties (bending strength), and free DDM. The results are shown in Table 2.

  In addition, when the gel time is spread on a hot plate kept at 200 ° C., a certain amount of the heat-resistant resin composition is formed into a circle having a diameter of 4 to 5 cm, and kneaded at a constant speed, the heat-resistant resin composition increases in viscosity. The time when the stickiness disappeared was measured. The viscosity was measured at 150 ° C. using a HaKKe rotational viscometer.

  In the aluminum plate adhesion test, a test piece of 5 mm × 5 mm × 5 mm was prepared using a heat resistant resin composition, and this was bonded to an aluminum plate to measure the tensile strength. As the 5% weight loss temperature, TG-DTA (manufactured by Seiko Instruments Inc.) was used, and the temperature at which the weight loss was 5% was measured at a heating rate of 20 ° C./min. The bending strength was measured based on JISK6911, and the free DDM was measured using gas chromatography.

  As is clear from Table 2, the heat-resistant resin compositions of the examples did not release 4,4-diaminodiphenylmethane like the heat-resistant resin compositions of the comparative examples, and the heat-resistant resin compositions of the comparative examples It was found that the adhesive property was excellent and the molding property, mechanical property and heat resistance were equivalent.

Claims (4)

(A) aminophenols having an amino group and a phenolic hydroxyl group in one molecule;
(B) a bisallylnadiimide type polyimide resin represented by the following chemical formula (1)

(In the formula, R represents a divalent group containing at least 2 carbon atoms.)
A heat-resistant resin composition characterized by comprising an essential component.   Of the (A) aminophenols having an amino group and a phenolic hydroxyl group in one molecule and (B) a total amount of 100% by weight of the bisallylnadiimide type polyimide resin represented by the chemical formula (1), (A 2. The heat resistant resin composition according to claim 1, wherein the content of aminophenols having an amino group and a phenolic hydroxyl group in one molecule is 5 to 20% by weight. (A) aminophenols having an amino group and a phenolic hydroxyl group in one molecule;
(B) a bisallylnadiimide type polyimide resin represented by the following chemical formula (1);

(In the formula, R represents a divalent group containing at least 2 carbon atoms.)
(C) A heat-resistant resin composition comprising an epoxy resin as an essential component.   (A) Aminophenol having an amino group and a phenolic hydroxyl group in one molecule, (B) a bisallylnadiimide type polyimide resin represented by chemical formula (1) and (C) an epoxy resin in a total amount of 100% by weight Of these, (A) the content of aminophenols having an amino group and a phenolic hydroxyl group in one molecule is 5 to 20% by weight, and the content of (C) the epoxy resin is 5 to 20% by weight. The heat resistant resin composition according to claim 3.