JPH02206651A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable for electrical and mechanical parts, having extremely improved sliding characteristics in a high-load and high-speed range, improved heat resistance and mechanical properties by blending a thermosetting resin with a specific amount of aromatic polyamideimide particles. CONSTITUTION:(A) 100 pts.wt. thermosetting resin (e.g. phenol resin or epoxyacrylate resin) is blended with (B) 3-300 pts.wt., preferably 5-100 pts.wt. spherical particles of an aromatic polyamideimide shown by formula I [Ar is one or more groups selected from groups shown by formula II, formula III and formula IV (R is H, alkyl, alkoxy or halogen; X is O, CO, SO2 or CH2)] which is obtained by subjecting trimellitic acid chloride anhydride and >=0.8 logarithmic viscosity, having preferably <=100mum, especially 5-50mum average particle diameters to give a thermosetting resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a thermosetting resin composition. More specifically, the present invention relates to a thermosetting resin composition having good mechanical properties at high temperatures and excellent sliding properties suitable for electrical parts, mechanical parts, etc.

(Prior Art and its Problems) In recent years, synthetic resin products have been increasingly used as machine parts in place of metal products due to the need for lighter equipment and easier manufacturing and assembly. For example, many synthetic resin products are used in sliding members such as bearings.

In such sliding members, polyamide, polyacetal, fluororesin, etc. have conventionally been used as synthetic resins with good sliding properties. These are relatively low temperature, low load,
In the low to medium speed range, it satisfies the required sliding properties even without lubrication, but as the temperature rises to high loads and high speeds, seizures and resin flow (plastic deformation) occur, making it unsuitable for use. It was unbearable.

In order to improve these drawbacks, methods have been adopted to add inorganic powder, glass fiber, aromatic polyamide fiber, carbon fiber, etc. as a solid lubricant to thermosetting resin, but inorganic powder Adding materials in the form of fibers may cause fibrillation, cracking, bending, etc. during sliding, and accumulate a large amount of abrasion powder, reducing sliding properties. This was problematic.

On the other hand, a method of adding meta-oriented aromatic polyamide powder to a thermosetting resin as a solid lubricant is also already known.

For example, JP-A-59-227924, JP-A-60-1
No. 79418 and No. 63-6043 disclose compositions in which aromatic polyamide powder is added to a bismaleimide-based thermosetting resin together with a fluorine-based filler. However, in the method using meta-oriented aromatic polyamide powder, it has been found that so-called abnormal wear occurs in which the amount of wear increases rapidly at a certain period during sliding in a high-speed region. That is, when sliding at high speeds, meta-oriented aromatic polyamide cannot exhibit sufficient heat resistance, and essentially lacks hardness as a solid lubricant. It is presumed that abnormal wear begins to occur at some point.

(Problems to be Solved by the Invention) The present invention has been made in view of the above circumstances, and provides excellent sliding performance with a small coefficient of friction and without damaging the mating material during sliding in high-load and high-speed areas. The object of the present invention is to provide a lubricating resin composition that has dynamic properties and is excellent in heat resistance and material properties.

(Means for Solving the Problem) In order to achieve the above object, the present inventors focused on aromatic polyamideimide which has excellent heat resistance and mechanical properties,
As a result of intensive research, we have found that a composition containing a specific amount of aromatic polyamideimide particles in a thermosetting resin described below has excellent heat resistance, sliding properties under high loads and high speeds, and also has excellent material properties. It was discovered that a molded article can be obtained easily and efficiently, and the present invention was completed.

That is, the gist of the present invention is as follows.

A thermosetting resin composition or a thermosetting resin composition comprising 3 to 300 parts by weight of aromatic polyamideimide particles represented by the following formula to 100 parts by weight of a thermosetting resin. , R is hydrogen, an alkyl group, an alkoxy group, or a halogen, and X is -O-, -
Represents CO--502-, -CH□-.

The thermosetting resin used in the present invention refers to a resin that can undergo a crosslinking reaction by heating, light, radiation, etc., or a radical generator such as peroxide. Furthermore, specifically, phenolic resin, urea'M resin, melamine resin, melamine-phenol co-condensed resin, xylene-modified phenol resin, guanamine resin, urea-guanamine, co-condensed resin, amino resin, acetoguanamine resin, unsaturated Polyester resin, polyimide resin such as bismaleimide,
Examples include xylene resin, epoxy resin, epoxy acrylate resin, and the like. In the present invention, the exemplified resins may not only be used alone, but also copolymers and mixtures of two or more types can be used, and within the range that does not impede the purpose of the present invention, for example, polyethylene, It can also be used as a mixture with thermoplastic resins such as polypropylene, polyacetal, polyamide, etc.

The aromatic polyamideimide used in the present invention is a polymer having repeating units connected by an amide group and an imide group directly bonded to an aromatic ring,
Refers to something that satisfies the above formula.

Such aromatic polyamideimide is an aromatic tricarboxylic acid, trimellidic acid chloride anhydride, and corresponding aromatic diamines, such as metaphenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 414 ′
It can be easily obtained by low-temperature solution polymerization with diaminodiphenylsulfone and the like. Also, instead of the aromatic diamine, aromatic diisocyanates such as tolylene diisocyanate, naphthalene-2,6-diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, etc., and trimellitic acid or its It can be obtained by heating and reacting anhydride with an anhydride in an amide solvent such as N-methyl-2-pyrrolidone.

The degree of polymerization of the aromatic polyamideimide used in the present invention is not particularly limited, but a degree of polymerization of 0.8 or more in terms of logarithmic viscosity (η1nh) is usually used.

Particles can be obtained from such aromatic polyamide-imide by pulverizing the isolated and purified polymer using commonly used mechanical pulverizing means such as ball mills, hammer mills, jet mills, etc.

The aromatic polyamideimide particle size (representing the average particle size, hereinafter simply referred to as particle size) used in the present invention varies somewhat depending on the material of the other side when used as a sliding material, but is usually 100 μm or less. Those within this range are preferably used. In order to obtain especially high sliding properties, the particle size should be 5 to 50.
It is preferable to use particles in the μm range.

High sliding properties can be obtained regardless of the shape of the particles, such as spherical, scale-shaped, rod-shaped, etc., but in order to obtain particularly high sliding properties, a spherical shape is preferred.

The thermosetting resin composition of the present invention comprises the above-mentioned thermosetting resin 1.
It is important that the above-mentioned aromatic polyamideimide resin particles be added in an amount of 3 to 300 parts by weight per 00 parts by weight. If the amount of aromatic polyamide-imide resin particles is less than 3 parts by weight, sufficient sliding properties cannot be obtained, and if the amount is more than 300 parts by weight, high sliding properties cannot be obtained, but the sliding properties will actually decrease. Undesirable. If the blending ratio of aromatic polyamide-imide resin particles is within the range mentioned above, the wear coefficient will be small and excellent sliding properties can be exhibited even in high load and high speed areas. However, the blending ratio of aromatic polyamide-imide resin particles Particularly excellent sliding properties are exhibited when the amount is 5 to 100 parts by weight.

To prepare the thermosetting resin composition of the present invention, a thermosetting resin and aromatic polyamideimide particles can be mixed at the above-mentioned mixing ratio using conventional methods (known methods may be used; For example, there is a method of mixing thermoplastic resin powder and aromatic polyamideimide particles using a mixer such as a Henschel mixer, a ball mill, or a tumbler mixer.

The method of molding the composition of the present invention into, for example, a sliding material is not particularly limited, but usually, the mixed powder is first shaped by compressing it, and then heated and pressurized. A compression molding method of hardening molding is used. Further, depending on the case, it is also possible to perform extrusion molding or the like by mixing a thermoplastic resin, and it may be selected as appropriate depending on the purpose of use.

In addition to the thermosetting resin and the aromatic polyamide-imide particles, the thermosetting resin composition of the present invention contains additives that can be widely incorporated into synthetic resins as appropriate within the range that does not reduce the properties of the composition of the present invention. They can also be used together. Examples of such additives include, but are not limited to, mold release agents, flame retardants, weather resistance improvers, etc., and conventionally known and publicly used solid or liquid lubricants may be used in combination. Of course, it is possible to do so, and tetrafluoroethylene resin, graphite, graphite fluoride, talc, boron nitride, fluorine oil, silicone resin or oil, and other industrial lubricants can also be selected and used as appropriate depending on the purpose of use. can do. In any case, it is of course possible to modify the intermediate or final product to improve its properties by chemical or physical treatment, as long as the performance of the thermosetting resin composition of the present invention is not impaired.

(Function) In the thermosetting resin composition of the present invention, aromatic polyamideimide particles with excellent heat resistance and mechanical properties are finely dispersed to form a sliding contact surface, resulting in a small coefficient of friction and friction in the high-speed region. However, since the thermoplastic resin of the base material is reinforced, it is possible to obtain stable sliding characteristics for a long time with little wear.

(Examples) Hereinafter, the present invention will be explained in more detail and concretely using Examples.

Evaluation of friction and wear properties〉 Friction coefficient; surface pressure of 10 kg using precious wood type friction and wear tester
/eta, linear velocity 60 cm/sec, 50 hours, mating material 34
Measured without 5C oil.

Wear coefficient: Surface pressure of 2 kg/by lead dust type friction and wear tester
cIfl, linear velocity 60C1+1/sec, 50 hours, mating material 345C was measured without oil.

Reference Example 8.5 kg of lithium chloride and 19.8 kg of diaminodiphenylmethane were added and dissolved in 250 kg of N-methyl-2-pyrrolidone in a polymerization vessel equipped with a stirrer, and then powdered trimellitic anhydride chloride 21, 1 kg
were added all at once to carry out polymerization.

After continuing stirring for 3 hours, the obtained viscous polymerized dope was put into a Henschel mixer together with water and stirred for 30 minutes to coarsely crush it. After the coarse crushing was completed, the contents were taken out, washed with water and dried. Then, the obtained coarse material was heated at 270°C.
It was treated in a vacuum dryer of RR for 2 hours. Next, the obtained treated product was pulverized using a jet mill and then classified to obtain aromatic polyamideimide particles having an average particle size of 34 μm.

Examples 1 to 3 The aromatic polyamide-imide particles obtained in the reference example and Mirex 2410 powder manufactured by Mitsui Toatsu Co., Ltd. as a novolac type noenol resin were mixed at the mixing ratio shown in Table 1,
Then, a test piece was molded at a mold temperature of 180° C. and a curing time of 45 seconds.

Using this test piece, a friction and wear test was conducted and the results obtained are shown in Table 1.

For comparison, a molded test piece containing no aromatic polyamideimide powder was similarly prepared and evaluated.

The results are listed in Table 1, and it was proven that the molded product of the present invention was superior to these comparative examples in terms of both friction and abrasion properties.

Example 4 As a thermosetting resin, 1.25 gr of Kelimide@1000 powder manufactured by Rhone Poulenc and 37.5 gr of aromatic polyamideimide resin powder with an average particle size of 34 μm obtained in Reference Example were mixed. The obtained mixed powder was filled into a mold and heated at 300 kgi ctl at 230°C.
It was heated and cured for 15 minutes to form a test piece for evaluating friction and wear properties. This test piece had a coefficient of friction of 0.17 and a coefficient of wear of 0.13×10-” ci/kg-cu+, indicating extremely excellent friction and wear characteristics.

(Effects of the Invention) As is clear from the above explanation and examples, by blending a specific amount of aromatic polyamideimide particles into a thermosetting resin, the sliding characteristics in high load and high speed regions are significantly improved. As a result, a lightweight and high-performance sliding member can be obtained. Furthermore, the composition of the present invention has excellent heat resistance and mechanical properties, and has excellent and well-balanced properties.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Scope of Claims] A thermosetting resin composition characterized by blending 3 to 300 parts by weight of particles made of aromatic polyamideimide represented by the following formula with respect to 100 parts by weight of the thermosetting resin. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, in the above formula, Ar is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 1 selected from
or two or more kinds, R is hydrogen, an alkyl group, an alkoxy group, or a halogen, and X represents -O-, -CO-, -SO_2-, -CH_2-.