JP2879150B2 - Thermosetting resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermosetting resin composition used as a sliding portion material and having excellent sliding properties and heat resistance.

[Conventional technology]

Conventional thermosetting aromatic hydrocarbon resins mainly include a raw material mainly containing one or both of naphthalene and alkylnaphthalene and an aromatic compound having at least two hydroxymethyl groups or halomethyl groups. From the crosslinking agent as a component, in the presence of an acid catalyst,
It is synthesized by heating, heat resistance, mechanical properties,
It has been relatively recently developed as a resin having excellent electrical properties and moldability. However, such resins have remarkably inferior sliding properties such as lubricity and wear resistance.

Conventionally, a polyimide resin is generally widely used as a resin having excellent heat resistance, sliding characteristics, and mechanical characteristics. However, this resin cannot be said to have sufficient sliding characteristics.

[Problems to be solved by the invention]

Thus, resins having excellent heat resistance, mechanical properties, electrical properties, and moldability, particularly conventional thermosetting aromatic hydrocarbon resins, still have satisfactory sliding properties. There was a problem that it was not done, and it was an issue to solve this.

[Means for solving the problem]

In order to solve the above-mentioned problems, the present invention relates to a thermosetting aromatic hydrocarbon resin, that is, a basic structure in which one or both of naphthalene and alkylnaphthalene are bonded by a methylene bond via one or more aromatic rings. Thermosetting resin (hereinafter abbreviated as COPNA resin)
Means for obtaining a resin composition in which graphite is added. The details are described below.

First, the COPNA resin in the present invention is prepared, for example, by the method disclosed in JP-A-62-522, that is, a raw material containing one or both of naphthalene and alkylnaphthalene as a main component and at least two raw materials. A cross-linking agent containing an aromatic compound having a hydroxymethyl group or a halomethyl group as a main component is represented by the following formula: 1.1 × 1 / n ≦ (W ₂ / W ₁ ) × (a / b) ≦ 6 × 1 / n ( In the formula, W ₁ is the weight of the raw material, W ₂ is the weight of the crosslinking agent, a
Is the molecular weight or average molecular weight of the raw material, b is the molecular weight or average molecular weight of the crosslinking agent, n is the number of hydroxymethyl groups or halomethyl groups bonded to 1 mole of the aromatic compound as the crosslinking agent, and 2 or more It is. And mixing the mixture in the presence of an acid catalyst to a temperature of 70 to 300 ° C. to form a thermosetting material consisting of an intermediate condensation reaction product of the mixture, or
For example, a method of heating to 350 ° C. to thermally cure the resin may be exemplified. However, in any case, for the purpose of facilitating molding, it is preferable to take out the COPNA resin in the pre-polymerization stage, add graphite and other fillers, and then further proceed with polymerization.

Next, the graphite in the present invention preferably has a flaky or plate-like shape, and particularly has a carbon purity of 99.9% by weight.
It is preferable that it is above. The amount of such graphite is 5 to 70% by weight, preferably 10 to 60% by weight, based on the total amount of the COPNA resin composition. This is because if the amount of graphite is less than 5% by weight, no improvement in the sliding properties can be expected, and if it is more than 70% by weight, the mechanical properties and moldability are inferior.

Various fillers can be added, for example, for the purpose of improving strength and imparting toughness, as long as the effects of the present invention are not impaired. The filler is organic or inorganic, and also has a fibrous, plate-like, granular,
Any shape such as a hollow shape may be used, and there is no particular limitation. In general, a fibrous material is used for replenishing strength, a plate-like material such as mica is used when dislike warpage, a granular material is used when isotropic strength is required, and a hollow spherical material is used when weight reduction is required. Good.

The method of mixing the above COPNA resin, graphite, and other fillers is not particularly limited.For example, after dry-mixing with a mixer or the like in advance, kneading with a roll or melt-mixing using a kneader or the like, and pulverizing. And granulation. Also, the molding method is not particularly limited, but may be formed by a normal molding method such as compression molding, transfer molding, or injection molding according to the shape of the molded product. Flow control or moisture,
Preliminary heat treatment at a temperature of 100 to 120 ° C. for 10 to 30 minutes may be performed to remove volatile components such as a solvent.

In order to completely cure the molded article and improve its heat resistance, mechanical properties, sliding properties, etc.,
The heat treatment may be performed at a temperature of 200 to 240 ° C. for 1 to 15 hours. Such a heat treatment is rather preferable.

[Action]

The added graphite lowers the coefficient of friction and reduces the amount of wear without impairing the inherent properties of the COPNA resin.
It shows a very favorable effect of significantly improving the sliding characteristics of the PNA resin.

〔Example〕

The raw materials used for the resin and the comparative examples are collectively shown as follows.

COPNA resin (manufactured by Sumikin Kako: SK resin), graphite (manufactured by LONZA: graphite powder KS44), ethylene tetrafluoride resin (hereinafter abbreviated as PTEE) (Kitamura: KTL600), molybdenum disulfide (hereinafter MoS ₂ Abbreviations] (manufactured by Dow Corning: Molycoat Z), carbon fibers (hereinafter abbreviated as CF) (manufactured by Kureha Chemical Industry: Kurekato T101T), Examples 1 and 2: After dry-mixing with a mixer, the temperature was adjusted to 80 with a roll kneader.
The mixture was melt-mixed at a temperature of 16 ° C. and a rotation speed of 16 to 20 rpm, pulverized by a pulverizer and granulated. After that, mold temperature 180 ~ 200 ℃, molding pressure 20
Under the condition of 0 to 500 kg / cm ² , heat compression molding is performed for 5 to 10 minutes, and a disk-shaped molded product having a diameter of 25 mm and a thickness of 12 mm and a length of 135 m
m, a width of 31 mm and a thickness of 4 mm were obtained. Then, at 230 ° C, 12
A heat treatment was performed for a long time, and processed for each physical property measurement to prepare a test piece.

In addition, each physical property was calculated | required by the following method, respectively.
And the obtained result was put together in the same table.

(1) Friction coefficient and wear amount: Wind speed 105m / min, load 1.2 using Savan type friction and wear tester
Under the condition of kg, the coefficient of friction after 2 hours and the amount of wear after 50 hours were measured.

(2) Flexural strength: Measured according to JIS-K7203.

(3) Heat deformation temperature: Measured according to JIS-K7203 (load 18.5 kgf / mm ² ).

Comparative Examples 1-4: Test pieces were prepared in the same manner as in Example 1 except that the mixing ratios of the raw materials were as shown in the table, and their physical properties were examined. The results were collectively shown in the table.

As is clear from the table, in Examples 1 and 2 to which graphite was added, the coefficient of friction was low, the amount of wear was small, and the sliding characteristics were extremely excellent. In both cases, both the coefficient of friction and the amount of wear are large, and are considerably inferior to those of Examples 1 and 2.

[Effect] The thermosetting resin composition of the present invention has a low coefficient of friction and excellent abrasion resistance, and has excellent sliding properties, heat resistance, and mechanical properties. It is the most suitable for the sliding part material used in the equipment-related industry, the electric / electronic equipment-related industry, and many other fields, and the effect is extremely large.

Continuation of front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 65/04 C08K 3/04

Claims (1)

(57) [Claims] (1) one or both of naphthalene and alkylnaphthalene is linked via one or more aromatic rings,
A thermosetting resin composition characterized in that graphite is added to an aromatic hydrocarbon resin having a basic structure linked by a methylene bond in an amount of 5 to 70% by weight based on the total amount.