JPH0632969A - Heat-resistant resin composition for molding - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in heat resistance and mechanical characteristics at high temperature and having excellent capability of sliding on a soft metal by compounding a specified thermosetting resin and a specified compound filler each in a specified amount. CONSTITUTION:This resin composition consists of: 30-70wt.% thermosetting resin composed essentially of an adduct of a polymaleimide of formula I (wherein R<1> is an n-valent organic group; X<1> and X<2> are each H, halogen or an organic group; and (n) is 2 or greater) to an aminophenol of formula II (wherein R<2> is X<1>; and m is 1 to 5), an epoxy compound having at least two epoxy groups in the molecule (e.g. bisphenol A epoxy resin), and a condensed polycyclic polynuclear aromatic resin (e.g. COPNA, a product of Sumikin Kako) obtained by crosslinking a condensed polycyclic aromatic hydrocarbon by p- xylene glycol in the presence of an acid catalyst; and 30-70wt.% compound filler containing 50-83wt.% fluororesin (e.g. TLP-10, a product of Mitsui Fluorochemicals) and 5-38wt.% aromatic polyamide powder (e.g. Cornex, a product of Teijin Ltd.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin composition for molding which has good heat resistance and mechanical properties at high temperatures, and particularly has excellent slidability with respect to soft metals such as aluminum and brass.

[0002]

Conventionally, asbestos fibers have been used as a base material used for molding materials and friction agents having excellent heat resistance. However, in recent years, asbestos has been banned because it is harmful. Regarding the slidability, carbon fibers are effective for hard metals such as steel, but carbon fibers have a problem of large wear and poor slidability for soft metals such as aluminum and brass. Further, thermosetting phenol resin and epoxy resin are mainly used as the binder resin, but the heat resistance is still poor and there is a limit to the use under high load conditions.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is a heat-resistant resin composition for molding which is excellent in heat resistance, mechanical properties at high temperatures, and slidability against soft metals. It is an attempt to provide something.

[0004]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that a resin composition comprising a thermosetting resin and a composite filler, which will be described later, achieves the above object. The inventors have found what can be achieved and completed the present invention.

That is, the present invention is based on the general formula (A) (a)

[0006]

[Chemical 3] (In the formula, R ¹ is an n-valent organic group, X ¹ and X ² are hydrogen atoms,
Same or different selected from halogen atom or organic group 1
A valence atom or group, n is an integer of 2 or more, respectively), and (b) a general formula

[0007]

[Chemical 4] (Wherein R ² represents a monovalent atom or group selected from a hydrogen atom, a halogen atom or an organic group, and m represents an integer of 1 to 5, respectively), and an addition reaction product with an aminophenol, (C) an epoxy compound having two or more epoxy groups in one molecule, and (d) a condensed polycyclic polynuclear aromatic resin obtained by crosslinking condensed polycyclic aromatic hydrocarbons with paraxylylene glycol using an acid catalyst. Thermosetting resin 30 as an essential component
~ 70 wt% and (B) (e) Fluorine resin 50-83 wt%
And 30 to 70% by weight of a composite filler containing (f) 5 to 38% by weight of an aromatic polyamide powder, which is a heat-resistant resin composition for molding.

The present invention will be described in detail below.

As the (a) polymaleimides, which is one of the essential components in the thermosetting resin (A) used in the present invention, those represented by the above general formula 3 are used. For example, ethylene bismaleimide, hexamethylene bismaleimide, m- or p-phenylene bismaleimide, 4,4'-diphenylmethane bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4 ′ -Dicyclohexylmethane bismaleimide, m- or p-xylylene bismaleimide, 4,4 ′
-Phenylene bismaleimide and the like are used, and these are used alone or in combination of two or more kinds. Further, if necessary, monomaleimides such as N-3-chlorophenylmaleimide and N-4-nitrophenylmaleimide can be used together with these polymaleimides.

As the following essential component (b) aminophenols, those represented by the above general formula 4 are used. For example, o-, m- or p-aminophenol, o-, m-
Or p-aminocresol, aminoxylenol containing various substituent isomers, aminochlorophenol, aminobromphenol, aminocatechol, aminoresorcin,
Examples thereof include aminobis (hydroxyphenol) propane and aminooxybenzoic acid, which may be used alone or in combination of two or more.

The above-mentioned (a) polymaleimides and (b) aminophenols are reacted to obtain an addition reaction product. The mixing ratio of each is 5 to 40 parts by weight of aminophenols based on 100 parts by weight of polymaleimides. It is desirable to add 10 parts by weight, more preferably 10 to 30 parts by weight. If the amount of aminophenols is less than 5 parts by weight, the compatibility of the addition reaction product with the (c) epoxy compound and (d) condensed polycyclic polynuclear aromatic resin described below is not sufficient, and conversely the amount of aminophenols is mixed. Is more than 40 parts by weight, the amino groups become excessive, and the heat resistance of the resin decreases, which is not preferable. The reaction temperature of the addition reaction product is generally 50 to 200 ° C, more preferably 80 to 18 ° C.
The reaction time is 0 ° C., and the reaction time can be arbitrarily selected in the range of several minutes to several tens hours depending on the reaction components.

Further, an essential component of the thermosetting resin
One (c) 1 epoxy compound having two or more epoxies in one molecule includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid glycidyl ester resin, and polyol. Polyglycidyl ether, urethane-modified epoxy resin, fatty acid or alicyclic polyepoxide obtained by epoxidizing an unsaturated compound, epoxy resin having a heterocycle, epoxy resin having a heterocyclic ring, epoxy resin having a glycidyl amine, and the like. , These may be used alone or in combination of two or more.

The condensed polycyclic polynuclear aromatic resin (d) which is one of the essential components in the thermosetting resin is a condensed polycyclic aromatic hydrocarbon such as naphthalene, anthracene, phenanthrene, pyrene, coal, coal tar pitch. Is a thermosetting resin obtained by cross-linking with paraxylylene glycol using an acid catalyst. As shown in the following chemical formula 5, the reaction is a condensed polycyclic aromatic nucleus that has progressed in the electrophilic substitution reaction accompanied by dehydration and has a structure in which a large number of benzylic bonds are linked as shown in the chemical formula 6. It is called an aromatic resin. Specific resins include COPNA (Condensed Polynuclear Aromatic)
Resin) (manufactured by Sumikin Kako Co., Ltd., trade name).

[0014]

[Chemical 5]

[0015]

[Chemical 6]

The mixing ratio of the polymaleimide-aminophenol addition reaction product, the epoxy resin and the condensed polycyclic polynuclear aromatic resin can be varied within a wide range depending on the use and purpose. The compounding ratio of the polymaleimide-aminophenol addition reaction product is 30 to 80% by weight in the thermosetting resin (A).
Can be included. If the proportion is less than 30% by weight, the heat resistance will be poor, and if it exceeds 80% by weight, the heat resistance will be sufficient but the mechanical strength will be reduced, such being undesirable. The order of mixing or reacting each of the above components is not particularly limited, and the thermosetting resin (A) having excellent curability and moldability and excellent heat resistance can be obtained. However, usually, first, an addition reaction product of (a) polymaleimides and (b) aminophenols is obtained, and (c) an epoxy compound and (d) a condensed polycyclic polynuclear aromatic resin are added thereto. (A) A thermosetting resin can be obtained.

The (B) composite filler used in the present invention is (e)
A product made of fluororesin and (f) aromatic polyamide powder is used. Examples of the (e) fluororesin include tetrafluoroethylene resin, fluorinated alkoxyethylene resin,
Examples thereof include fluorinated ethylene propylene ether resin, tetrafluoroethylene hexafluoropropylene copolymer resin, and calcined Teflon powder resin. Also used as other component (f)
Examples of the aromatic polyamide powder include Conex (trade name, manufactured by Teijin Ltd.). The aromatic polyamide powder preferably has a size of 30 mesh or more. The compounding ratio of the fluororesin and the aromatic polyamide powder is preferably 50 to 83% by weight of the fluororesin and 5 to 38% by weight of the aromatic polyamide powder in the composite filler. If it is less than 50% by weight of the fluororesin and less than 5% by weight of the aromatic polyamide powder, the slidability is not effective, and if it exceeds 83% by weight of the fluororesin and 38% by weight of the aromatic polyamide powder, the heat resistance is deteriorated. Further, as other components, graphite, molybdenum disulfide, boron nitride and the like can be mentioned. Particularly when heat resistance is required, graphite is not preferable, so it is appropriately selected and added. Further, as the internal release agent, carnauba wax, higher saturated fatty acid ester,
Examples include stearic acid and zinc stearate, which are added as necessary.

The heat-resistant resin composition for molding of the present invention is characterized by comprising 30 to 70% by weight of the above-mentioned (A) thermosetting resin and 30 to 70% by weight of (B) composite filler. But,
The blending ratio of these is limited to the above range because when the thermosetting resin is less than 30% by weight, workability and moldability are poor, and
If it exceeds 70% by weight, a molded product satisfying the required properties cannot be obtained. Further, the heat-resistant resin composition for molding of the present invention is thermosetting and is generally cured by heating to a temperature of 150 to 250 ° C., but various additives may be added as necessary to obtain various properties. Can be further improved.
For example, known acid anhydrides, boron fluoride complexes, tertiary amines, imidazoles, quaternary ammonium salts, and peroxide curing catalysts can be added to further improve the curability.

[0019]

The heat-resistant resin composition for molding of the present invention has excellent heat resistance, mechanical properties, and sliding properties when the thermosetting resin is 30 to 70% by weight and the composite filler is 30 to 70% by weight. It was possible to gain motility. That is, heat resistance and mechanical properties are secured by setting a predetermined ratio of the addition reaction product in the thermosetting resin, and by defining the compounding ratio of the fluororesin and the aromatic polyamide powder in the composite filler, It has excellent heat resistance and slidability.

[0020]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Examples 1-6 4,4'-diphenylmethane bismaleimide, m-aminophenol, epoxy resin, condensed polycyclic polynuclear aromatic resin, 2-
Each of the compounding components of ethyl-4-methylimidazole was selected in the weight composition ratio shown in Table 1 to synthesize a thermosetting resin. A composite filler was added to the obtained thermosetting resin in a weight composition ratio shown in Table 1 and uniformly mixed by stirring to produce a heat-resistant resin composition for molding.

Comparative Examples 1 to 4 Thermosetting resins and heat-resistant resin compositions for molding were produced in the same manner as in the examples with the weight composition ratios shown in Table 2.

[0023]

[Table 1] * 1: Dow Chemical's novolac type epoxy resin,
Product name. * 2: Bisphenol A epoxy resin manufactured by Shell Chemical Co., Ltd., trade name. * 3: Powdered fluororesin manufactured by Mitsui Fluorochemicals, trade name. * 4: Fired powder fluororesin manufactured by Kitamura Co., trade name. * 5: Teijin's aromatic polyamide powder, trade name. * 6: Natural graphite graphite manufactured by Nippon Graphite Co., Ltd., trade name. * 7: Dow Corning molybdenum disulfide, trade name.

[0024]

[Table 2] * 1: Dow Chemical's novolac type epoxy resin,
Product name. * 2: Bisphenol A epoxy resin manufactured by Shell Chemical Co., Ltd., trade name. * 3: Powdered fluororesin manufactured by Mitsui Fluorochemicals, trade name. * 4: Fired powder fluororesin manufactured by Kitamura Co., trade name. * 5: Teijin's aromatic polyamide powder, trade name. * 6: Natural graphite graphite manufactured by Nippon Graphite Co., Ltd., trade name. * 7: Dow Corning molybdenum disulfide, trade name.

The heat-resistant resin compositions for molding obtained in Examples 1 to 6 and Comparative Examples 1 to 4 were heated at a temperature of 200 to 200 by a pressure molding machine.
220 ℃, pressure 100 ~ 300 kgf / cm ² for 1 ~ ² min / mm molding time, pressure molding, then 200 ~ 230 ℃,
Molding for various tests was made by carrying out a curing treatment for 5 to 15 hours. Mechanical properties of this test molded article were measured according to JIS-K.
It measured according to -6911. Also, regarding sliding characteristics, the measurement conditions were 2 cm ² (outer diameter 2
Cylindrical with 5.6φ, 20.0φ inner diameter, 3S finish) with a sliding area of aluminum (A5052-BD), no lubrication, sliding speed 1m / sec, pressure load 10-50kgf / cm
^The dynamic friction coefficient was calculated at ² (cumulative load after 10 minutes of operation at 10 kgf / cm ² ). In addition, the sliding speed is 0.3 cm / sec and the load is 10 kgf /
The amount of wear was measured after continuously operating for 24 hours under the condition of cm ² . These results are shown in Tables 3 and 4, and the remarkable effect of the present invention was confirmed.

[0026]

[Table 3]

[0027]

[Table 4] * 1: The temperature rise due to the coefficient of dynamic friction and frictional heat is significant, and seizure is noticeable on the sliding surface after measurement, and the amount of wear is large. * 2: The sample was damaged during measurement due to its poor mechanical strength. * 3: Sliding surface seizure stopped operation halfway. * 4: The coefficient of dynamic friction is large and there is a great deal of variation.
k unstable.

[0028]

As is clear from the above description and Tables 3 and 4, the heat-resistant resin composition for molding of the present invention has excellent heat resistance, mechanical properties at high temperatures, sliding properties, especially aluminum, It has excellent sliding properties against soft metals such as brass, good workability and moldability, and can be used in a wide range of applications such as sliding materials, friction materials, and electrical insulating materials.

Claims (1)

[Claims] 1. (A) (a) general formula: (In the formula, R ¹ is an n-valent organic group, X ¹ and X ² are hydrogen atoms,
Same or different selected from halogen atom or organic group 1
A valence atom or group, n is an integer of 2 or more), and (b) the general formula: (Wherein R ² represents a monovalent atom or group selected from a hydrogen atom, a halogen atom or an organic group, and m represents an integer of 1 to 5, respectively), and an addition reaction product with an aminophenol, (C) an epoxy compound having two or more epoxy groups in one molecule, and (d) a condensed polycyclic polynuclear aromatic resin obtained by crosslinking condensed polycyclic aromatic hydrocarbons with paraxylylene glycol with an acid catalyst. Composite filler 30 containing 30 to 70% by weight of thermosetting resin as an essential component, (B) 50 to 83% by weight of (e) fluororesin, and (f) 5 to 38% by weight of aromatic polyamide powder 30
A heat-resistant resin composition for molding, characterized in that the heat-resistant resin composition comprises 70 to 70% by weight.