JP3044468B2 - Sliding resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition having excellent slidability. In particular, the present invention relates to a slidable resin composition that can be used under severe conditions, in which a mating material is a metal and is used in a high-speed and high-load sliding portion (of course, a high temperature is generated by frictional heat).

[Related Art] In recent years, synthetic resin products have come to be used as a large number of mechanical parts in order to reduce the weight of machines and reduce product costs, and synthetic resin products are often used for parts requiring slidability. I have.

Conventionally, as a resin composition having good slidability, additives such as polyamide, polyacetal, polyphenylene sulfide, polytetrafluoroethylene and the like for improving the sliding properties of solid lubricants, lubricating oils and the like were added to resins such as polytetrafluoroethylene. Things have been used.

These can be used without any problem in the relatively low load and low speed areas, but as the load increases and the speed increases, they are more likely to be worn, and they cannot be used due to seizure or melting due to frictional heat . For this reason, wear resistance,
For the purpose of improving heat resistance, glass fiber, carbon fiber, various whiskers, etc. are added, but these fillers have a problem that they cause the metal and resin of the mating material used for the sliding portion to be worn. .

In other words, the sliding characteristics required for high-load, high-speed sliding parts are different from conventional sliding characteristics, such as abrasion resistance, heat resistance, and other physical properties rather than the coefficient of friction. The material must be selected from a completely different point of view.

On the other hand, thermotropic liquid crystal polymers having a high melting point have a high heat resistance among many plastics, and therefore are less likely to burn or melt due to frictional heat.

However, usually, the mating material of the sliding portion is made of a metal material such as aluminum alloy and steel, but the thermotropic liquid crystal polymer itself has poor abrasion resistance with respect to these metals. There was no example used for a suitable sliding material.

By the way, the present inventors have found that so-called vitreous carbon, which is characterized by a particle fracture surface having a vitreous luster, is effective as an additive for solving the above-mentioned problems of thermotropic liquid crystal polymer. Due to the fact that carbon is produced by carbonizing thermosetting resins such as phenolic resins, they may contain incomplete or uncarbonized materials.

That is, even if the fracture surface has been confirmed to have a glassy gloss or to have a broad peak at a specific diffraction angle in an X-ray diffraction spectrum, the glassy carbon is incompletely carbonized or not. It may contain carbonized material.

When blending glassy carbon into a thermoplastic resin, the presence of incomplete carbonized or uncarbonized products as described above often does not pose a problem in the molding process of the thermoplastic resin or the molded product itself. . That is, these incompletely carbonized or uncarbonized products are considered to be the thermosetting resin itself, which is the raw material resin for glassy carbon, or a thermally decomposed low polymer thereof.

However, the forming temperature of the thermotropic liquid crystal polymer is extremely high because one of its features is a high melting point which can be said to be abnormal in the polymer. In such a case, the incomplete carbonized material or uncarbonized material contained in the glassy carbon is likely to decompose and cause gas generation. At high temperatures, especially in molding under high pressure, such as compression or injection molding, the generation of gas, even a small amount of gas generation, can be a fatal defect in the working process or in the molding. For example, in an extreme case, molding itself is difficult due to gas generation, or blisters are observed on the surface of the molded product, and the commercial value of the molded product is lost.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems, and in particular, a sliding which has excellent wear resistance, is easily heat-resistant, and has commercial value as a molded product. An object of the present invention is to provide a conductive resin composition.

[Means for Solving the Problems] That is, the present invention relates to a thermotropic liquid crystal polymer (a) which is a (co) polymer containing at least a monomer unit represented by the following formula: 90 to 30% by weight, And 10 to 70% by weight of spherical glassy carbon (b) having a weight loss of not more than 5% by weight when held at 350 ° C. for 30 minutes in air characterized by a particle-like cross-section having a glassy luster. It relates to a slidable resin composition characterized by the above.

 Hereinafter, the present invention will be described in detail.

The thermotropic liquid crystal polymer referred to in the present invention is a thermoplastic meltable polymer that exhibits optical anisotropy when melted. Such a polymer exhibiting optical anisotropy at the time of melting has a property that polymer molecular chains take a regular parallel arrangement in a molten state. The properties of the optically anisotropic molten phase are
It can be confirmed by a normal polarization inspection method using an orthogonal polarizer.

Thermotropic liquid crystal polymers are generally made from monomers that are elongated, flattened, and have a plurality of chain extension bonds in either a coaxial or parallel relationship that are rigid along the long chain of the molecule.

The thermotropic liquid crystal polymer used in the present invention includes:
A polymer in which a part of one polymer chain is composed of a segment of a polymer forming an anisotropic molten phase and the remaining part is composed of a segment of a thermoplastic resin not forming an anisotropic molten phase is also included. Further, a composite of a plurality of thermotropic liquid crystal polymers is also included.

In the present invention, among the thermotropic liquid crystal polymers, a polymer or a copolymer containing an oxybenzoyl group represented by the above formula as a monomer unit is used. This material has particularly high heat resistance and is preferable as a sliding material.

More preferred among the above (co) polymers are wholly aromatic polyesters containing an oxybenzoyl group.

The constituent components of the wholly aromatic polyester forming the optically anisotropic molten phase as described above include (A) at least one kind of aromatic dicarboxylic acid and alicyclic dicarboxylic acid compound, and (B) aromatic hydroxycarboxylic acid. (C) aromatic diol, alicyclic diol, at least one aliphatic diol compound, (D) aromatic dithiol, aromatic thiophenol, aromatic thiol carboxylic acid compound And at least one of (E) an aromatic hydroxyamine and an aromatic diamine compound. Although these may be constituted independently, in many cases (A), (C) and (A)
And (D), (A) (B) and (C), (A) (B) and (E), or (A) (B) (C) and (E). .

Examples of the (A1) aromatic dicarboxylic acid compound include terephthalic acid, 4,4'-diphenyldicarboxylic acid, and 4,4'-
Triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'dicarboxylic acid, Diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenylether-3,3'-dicarboxylic acid, diphenoxyethane-3,3'dicarboxylic acid, diphenylethane- 3,3'-dicarboxylic acid, aromatic dicarboxylic acid such as 1,6-naphthalenedicarboxylic acid or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, ethylterephthalic acid, methoxyterephthalic acid, Alkoxy and alkoxy of the above aromatic dicarboxylic acids such as ethoxy terephthalic acid Or halogen-substituted derivatives thereof.

(A2) As the alicyclic dicarboxylic acid, trans-1,4
An alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or trans-1,4- (2
-Methyl) cyclohexanedicarboxylic acid, trans-1,
Alkyl, alkoxy or halogen-substituted products of the above alicyclic dicarboxylic acids such as 4- (2-chloro) cyclohexanedicarboxylic acid.

(B) As the aromatic hydroxycarboxylic acid compound,
4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6
-Hydroxy-2-naphthoic acid, 6-hydroxy-1-
Aromatic hydroxycarboxylic acids such as naphthoic acid or 3-
Methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4
-Hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid,
3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid, 2-chloro-4-hydroxybenzoic acid, 3- Chloro-4-hydroxyamine benzoic acid, 2,3-dichloro-4-hydroxybenzoic acid,
3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy -7-chloro-2-naphthoic acid,
Alkyl, alkoxy or halogen-substituted aromatic hydroxycarboxylic acids such as 6-hydroxy-5,7-dichloro-2-naphthoic acid.

(C1) As aromatic diols, 4,4'-dihydroxydiphenyl, 3,3'-dihydroxydiphenyl, 4,4 '
-Dihydroxytriphenyl, hydroquinone, resorcinol, 2,6-naphthalenediol, 4,4'-dihydroxydiphenylether, bis (4-hydroxyphenoxy) ethane, 3,3'-dihydroxydiphenylether, 1,6-naphthalenediol, Aromatic diols such as 2-bis (4-hydroxyphenyl) propanebis (4-hydroxyphenyl) methane or chlorohydroquinone, methylhydroquinone, t-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, Alkyl-, alkoxy-, or halogen-substituted aromatic diols such as -methylresorcin;

(C2) As the alicyclic diol, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanedimethanol, cis-1,4-cyclohexanedimethanol, trans- Alicyclic diols such as 1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexanedimethanol or trans-1,2
Alkyl, alkoxy or halogen-substituted alicyclic diols such as 4- (2-methyl) cyclohexanediol and trans-1,4- (2-chloro) cyclohexanediol can be mentioned.

(C3) Examples of the alicyclic diol include linear or branched aliphatic diols such as ethylene glycol, 1,3-propanediol diol, 1,4-butanediol, and neopentyl glycol.

(D1) As the aromatic dithiol, benzene-1,4-
Examples thereof include dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol.

(D2) Examples of the aromatic thiophenol include 4-mercaptophenol, 3-mercapton phenol, and 6-mercapton phenol.

(D3) Examples of the aromatic thiolcarboxylic acid include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, and 7-mercapto-2-naphthoic acid.

(E) Examples of aromatic hydroxyamine and aromatic diamine compounds include 4-aminophenol and N-methyl-4-.
Aminophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine, N, N'-dimethyl-1,
4-phenylenediamine, 3-aminophenol, 3-
Methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-
Hydroxydiphenyl ether, 4-amino-4'-hydroxydiphenylmethane, 4-amino-4'-hydroxydiphenylsulfide, 4,4'-diaminophenylsulfide (thiodianiline), 4,4'diaminodiphenylsulfone, 2,5-diamino Toluene, 4,4'-ethylenedianiline, 4,4'-diaminodiphenoxyethane, 4,4'-diaminodiphenylmethane (methylenedianiline), 4,4'-diaminodiphenylether (oxydianiline) and the like. .

Incidentally, a wholly aromatic polyester generally indicates a polyester substantially obtained from an aromatic carboxylic acid and an aromatic alcohol, but the wholly aromatic polyester of the present invention includes:
The above-mentioned segment portion which does not form the anisotropic molten phase also includes those formed of an ester with an aliphatic or alicyclic acid or alcohol. Further, the polyester itself or the segment forming the anisotropic molten phase also includes those composed of an ester with an aliphatic or alicyclic acid or alcohol as long as they form the anisotropic molten phase. You.

As a specific wholly aromatic polyester, Etc.

Further, the glassy carbon in the present invention has a turbostratic structure with an extremely small crystal size as a basic structure, and has a non-oriented structure as a fine structure.
It is produced by carbonizing a thermosetting resin such as a phenol resin, a furan resin, an epoxy resin, an unsaturated polyester resin, a urea resin, a melamine resin, an alkyd resin, and a xylene resin at a high temperature.

This vitreous carbon is characterized by having a fractured surface having a vitreous luster, but also has a diffraction angle (2θ) of 23 to 25 in a spectrum in a normal X-ray diffraction method.
It is also confirmed by having a broad peak near the degree. The X-ray diffraction method is measured by a Cu-Kα ray (double line) according to a conventional method.

A conventional carbon material such as graphite does not have such a wide peak, but shows a sharp _d002 peak due to crystallinity at another diffraction angle (2θ = 26.4 °). It is preferable that the glassy carbon of the present invention has substantially no peak characteristic of graphite. In addition, a mere organic carbonized material does not have a glassy gloss in the fractured surface, and of course, does not have a peak at a specific diffraction angle characteristic of graphite as well as the glassy carbon in its X-ray diffraction spectrum.

Here, even if the fracture surface is glassy carbon characterized by having a glassy luster, the type of raw material resin, its preparation method, raw material particle shape, carbonization temperature, carbonization time,
Different properties are produced depending on the type of atmospheric gas, the pressure during carbonization, and other carbonization conditions. That is, the content and properties of the incompletely carbonized or uncarbonized material in the produced glassy carbon are different.

In the present invention, it is important to use a spherical glassy carbon having a weight loss of 5% by weight or less under the conditions specific to the liquid crystal polymer in view of the fact that the compound is mixed with the thermotropic liquid crystal polymer having a high melting point as described above. It is.

Here, the measurement of the weight loss is defined as a weight loss when heating is performed from room temperature to 350 ° C. at a heating rate of 10 ° C./min and held at that temperature for 30 minutes using, for example, a thermobalance as a measuring device. Vitreous carbon produced at carbonization temperatures typically above 800 ° C. has a weight loss of 5% by weight or less.

The glassy carbon having a weight loss of more than 5% by weight under the above conditions generates gas by heating at the time of molding in combination with the thermotropic liquid crystal polymer having a high melting point in the present invention (uncarbonized thermosetting). This is thought to be due to the decomposition of the water-soluble resin), molding becomes difficult, the appearance of the molded product deteriorates, blisters, etc., and the productivity and the commercial value are lowered.

On the other hand, the shape is preferably spherical, and more preferably close to a true sphere. A non-spherical shape such as an irregular shape is not preferable because, for example, a metal or resin of a mating material used for a sliding portion is worn.

The addition amount of spherical glassy carbon is 10 to 70% by weight.
And preferably 25 to 40% by weight. In this range, the abrasion resistance and the like are sufficient, and the effects of the present invention can be exhibited.

If the amount of the spherical glassy carbon is less than 10% by weight, the wear resistance is insufficient. Even if the amount exceeds 70% by weight, further improvement of the wear resistance cannot be expected. Further, the strength of the obtained molded article is also reduced.

In many cases, lubricating oil or the like is used as a lubricant in the sliding portion, and these are inactive at normal temperature, but may show corrosion properties to the contact members other than at high temperatures due to frictional heat. In addition, since the compressor is exposed to chemicals such as chlorofluorocarbon, resistance to these chemicals is also a problem.

However, the resin composition comprising the thermotropic liquid crystal polymer and the spherical glassy carbon in the present invention has sufficient chemical resistance at high temperatures, and therefore lubricates even at high temperatures when lubricating oil is used for the sliding part. It is not affected by oils or other drugs.

Here, various additives can also be blended in the composition of the present invention.

Additives include inorganic fillers, organic fillers, stabilizers, UV absorbers, pigments, dyes, modifiers, and the like. Of these, inorganic fillers are particularly important, and are often used for improving workability, physical properties, and the like.

As the inorganic filler, graphite, molybdenum disulfide, bronze, tank, mica, relay, sericite, calcium carbonate, calcium silicate, calcium phosphate, calcium pyrophosphate, silica, alumina, aluminum hydroxide, calcium hydroxide, graphite fluoride, Examples include potassium titanate, calcium phosphate, calcium pyrophosphate, and the like. Glass fibers, carbon fibers, various whiskers, and the like can be added as long as the effects of the present invention are not impaired.

In addition, as the organic filler, various thermoplastic or,
Thermosetting resins can be used, and fluorine resins are particularly preferably used.

The method of mixing the thermotropic liquid crystal polymer with the spherical glassy carbon or the additive added thereto is not particularly limited, and various means can be applied.

For example, they may be separately supplied to an extruder and melt-mixed, or may be preliminarily mixed by a mixer such as a Henschel mixer or a tumbler and then supplied to the extruder.

In addition, the glassy carbon particles of the present invention can be added during the polymerization of the thermotropic liquid crystal polymer.
Even in the case of a thermotropic liquid crystal polymer composition in which glassy carbon is blended at the time of polymerization as described above, naturally, when a processed product is produced therefrom, that is, the composition is formed by molding such as injection molding or compression molding. When molding, the thermotropic liquid crystal polymer is melt-molded and exposed to a high temperature. Therefore, even in such a case, the predetermined effect of the present invention is achieved.

The composition of the present invention thus obtained is molded by a method such as injection, compression, or extrusion.However, in the case of compression molding, in the case of compression molding, each is dry-blended in powder form, It may be molded.

The composition of the present invention has excellent slidability and abrasion resistance.
Various gears, cams, bearings, guide rolls for video tapes and cassette tapes, end face materials for mechanical seals, valve seats for valves, etc., sealing members such as V-rings, rod packing, piston rings, rider rings, rotary shafts for compressors, etc. It can be used for rotating sleeves, pistons, impellers, vanes, rotors, rollers, etc.

[Effect of the Invention] The composition of the present invention is most suitable as a sliding material used for a high-load, high-speed sliding part in which a mating material is a metal because it has the following characteristics.

(1) Since a polymer having a particularly high melting point is used among conventional plastics, melting, seizure, and the like due to frictional heat are less likely to occur.

(2) Since a specific glassy carbon is used, a material having little wear can be obtained, and a metal material such as iron, such as steel, which is a mating member of the sliding material, is hardly damaged.

(3) In the injection molding of the composition of the present invention, since the thermotropic liquid crystal polymer is used, it has a high melting point but has good fluidity at the time of melting, so that molding is easy.

(4) At high temperatures due to frictional heat, lubricating oil, chlorofluorocarbon, and the like, which should normally be inert, may show corrosiveness to members that come into contact therewith. However, since the composition of the present invention is stable against these, it is a suitable composition as a sliding material.

[Examples] The present invention will be described in more detail with reference to examples. However, these examples do not limit the scope of the present invention, but show preferred embodiments of the present invention.

First, raw materials used in Examples and Comparative Examples are collectively shown.

Thermotropic liquid crystal polymer A: terephthalic acid, 4-hydroxybenzoic acid, and 4,
A powder of thermotropic liquid crystal polymer (trade name: Zyder, manufactured by Amoco Performance Products Co., USA), which is a terpolymer of 4'-dihydroxydiphenyl. 420 ° C.

B: Thermotropic liquid crystal polymer which is a quaternary copolymer of terephthalic acid, isophthalic acid, 4-hydroxybenzoic acid and 4,4'-dihydroxydiphenyl (trade name: Zyder, manufactured by Amoco Performance Products, USA) Stuff Melting point 350 ° C.

Spherical glassy carbon AD is spherical glassy carbon obtained by firing and carbonizing a thermosetting resin.

A: Bellpearl C-800 (brand name) B: Univex GCP-50 (H) (same as above) C: Bellpearl C-2000 (same as above) D: Univex GCP-50 (L) (same as above) Bellpearl ... Kanebo ( The weight loss and the average particle size of each are as follows.

Weight loss 1.2%, average particle size 10 micron meter 〃 0.5%, 〃 30 micrometer 〃 0.2%, 以下 less than 10 micrometer 〃 5.1%, 〃 30 micrometer In all cases, the fracture surface of carbon particles has clear glassy gloss It was confirmed that the X-ray diffraction spectrum measured by Cu-Kα ray (double line) had a clearly broad peak around the diffraction angle (2θ) of 23 to 25 degrees. The A, in the glassy carbon particles B and D, sharp peak graphite specific but was not substantially observed, d ₀₀₂ peaks at the diffraction angle 2 [Theta] = 26.4 ° to the carbon of C was observed in the shoulder manner .

Weight loss: The temperature is raised from room temperature to 350 ° C at a rate of 10 ° C / min.
Weight loss when held at this temperature for 30 minutes. (Measured using a thermobalance SSC-5020 TG / DTA200 manufactured by Seiko Denshi Kogyo Co., Ltd.) Graphite AGP (trade name) flaky graphite manufactured by Nippon Graphite Co., Ltd. Average particle size: 10 μm Glass fiber Milled glass manufactured by Asahi Fiberglass Fiber
MFA diameter: 10 to 15 μm Average length: 30 to 100 μm Example 1 The above-mentioned raw materials were blended in the proportions shown in Table 1 and mixed with a Henschel mixer. : PCM-45 type) and melt-kneaded (temperature: 420 ° C, screw rotation speed: 200 rpm) and pelletized.

Next, the pellets are injected into an injection molding machine (TOSHIBA MACHINE: IS80E
PN-3Y type), cylinder temperature 410 ° C, injection pressure 1000kgf
A disc having a diameter of 5 cm and a thickness of 3 mm was formed under the conditions of / cm ² and a mold temperature of 180 ° C. The obtained test piece was subjected to a Suzuki-type friction and wear tester at a pressure of 5 kgf / cm ² and a speed of 20 m / min.
Using a ring-shaped S45C steel or aluminum having a diameter of 25.6 mm and an inner diameter of 20 mm, the wear coefficient and the wear amount of the mating material were measured.

Further, using the injection molding machine described above, a bending test piece was molded under the same conditions, and ASTM D-790 was obtained using the obtained test piece.
, The bending strength was measured. In addition, the moldability and the appearance were observed with ten test pieces at the same time. Hereinafter, moldability and appearance were similarly determined using ten test pieces.

Example 2 The above-mentioned various raw materials were blended in the proportions shown in Table 1, mixed with a Henschel mixer, and then melt-kneaded with a twin-screw extruder (PCM-45 type, manufactured by Ikegai Ironworks Co., Ltd., at a temperature of 350 ° C). The screw was rotated at 200 rpm) and pelletized.

Next, the pellets are injected into an injection molding machine (TOSHIBA MACHINE: IS80E
PN-3Y type), cylinder temperature 360 ° C, injection pressure 1000kgf
A disc having a diameter of 5 cm and a thickness of 3 mm was molded under the conditions of / cm ² and a mold temperature of 150 ° C., and the wear characteristics were measured as in Example 1.

Further, using the injection molding machine described above, a bending test piece was molded under the same conditions, and ASTM D-790 was obtained using the obtained test piece.
, The bending strength was measured. At the same time, the moldability and the appearance of the test piece were observed.

Example 3 The above-mentioned raw materials were blended at the ratios shown in Table 1, mixed with a Henschel mixer, and then melt-kneaded with a twin-screw extruder (PCM-45 type, manufactured by Ikegai Iron Works Co., Ltd., at a temperature of 420 ° C). The screw was rotated at 200 rpm) and pelletized.

Next, the pellet was compression-molded at a temperature of 420 ° C. and a pressure of 200 kgf / cm ² to prepare a test piece having a thickness of 3 mm and a size of 50 × 50 mm, and the wear characteristics were similarly evaluated. In addition, a flat plate with a thickness of 3 mm and a size of 100 x 100 mm was created, and a width of 12.7 mm and a length of
A 100 mm test piece was cut out and the bending strength was measured according to ASTM D-790. At the same time, the moldability and the appearance of the test piece were observed.

Example 4 The above-mentioned various raw materials were blended in the proportions shown in Table 1, mixed with a Henschel mixer, and then melt-kneaded with a twin-screw extruder (PCM-45 type, manufactured by Ikegai Iron Works Co., Ltd., at a temperature of 350 ° C). The screw was rotated at 200 rpm) and pelletized.

Next, the pellet was compression-molded at a temperature of 360 ° C. and a pressure of 200 kgf / cm ² to prepare a test piece having a thickness of 3 mm and a size of 50 × 50 mm, and the wear characteristics were similarly evaluated. In addition, a flat plate with a thickness of 3 mm and a size of 100 x 100 mm was created, and a width of 12.7 mm and a length of
A 100 mm test piece was cut out and the bending strength was measured according to ASTM D-790. At the same time, the moldability and the appearance of the test piece were observed.

 The above results are summarized in Table 1.

The bending test pieces obtained in Examples 1 to 4 were put into a 500 cc pressure-resistant container together with 150 ml of Suniso 4G oil, sealed, and further cooled, 500 g of Freon gas S-3 was injected. This pressure vessel is immersed in silicone oil at 165 ° C for 48 hours, cooled for 4 hours, degassed, and a sample is taken out.
The dimensional change and weight change in the length direction were measured.

All of the bending test pieces showed no dimensional change and no change in weight, indicating that the composition comprising the thermotropic liquid crystal polymer and glassy carbon had excellent chemical resistance.

Comparative Examples 1, 4, and 6 The above-mentioned raw materials were blended in the proportions shown in Table 2 and
In the same manner as in Example 1, pellet granulation, forming of a disk and bending test pieces were performed and evaluated. The results are shown in Table 2.

Comparative Example 2 The above-mentioned raw materials were blended in the proportions shown in Table 2 and
In the same manner as in Example 1, pellet granulation, forming of a disk and bending test pieces were performed and evaluated. The results are shown in Table 2.

Comparative Examples, 5, 7 The above ingredients were blended in the proportions shown in Table 2 and
Pellet granulation and flat plate molding were performed in the same manner as described above.
The results are shown in Table 2.

Here, in Examples 1 to 4, since the ratio of the thermotropic liquid crystal polymer to the spherical glassy carbon and the weight loss of the glassy carbon at 350 ° C. are all within the desired ranges, the abrasion characteristics, mechanical strength, moldability, and molded product are obtained. All of the appearances are excellent.

On the other hand, in Comparative Examples 1 to 3, graphite and glass fiber, which have been conventionally used for improving the slidability and wear resistance, were used, but the wear coefficient was large. The value of the quantity is also large. Particularly in terms of wear of the mating material, the difference is remarkable in the case of soft aluminum.

In Comparative Example 4, the abrasion resistance is insufficient because the spherical glassy carbon is less than 10% by weight. Further, in Comparative Example 5, the mechanical strength was insufficient because the amount of spherical glassy carbon exceeded 70% by weight.

Further, in Comparative Examples 6 and 7, since the weight loss of glassy carbon at 350 ° C. in air exceeded 5% by weight, generation of gas adversely affected moldability and appearance of molded articles. That is, in Comparative Example 6, a phenomenon was observed in which, during the injection molding, the resin nose dripping occurred while firing from the nozzle after measuring the resin. In addition, flow marks and blisters were generated in the obtained molded product. In Comparative Example 7, molding was impossible due to generation of gas.

Claims (4)

(57) [Claims] 1. A thermotropic liquid crystal polymer (a) which is a (co) polymer containing at least a monomer unit represented by the following formula: 90 to 30% by weight, And 10 to 70% by weight of spherical glassy carbon (b) having a weight loss of not more than 5% by weight when held at 350 ° C. for 30 minutes in air characterized by a particle-like cross-section having a glassy luster. A slidable resin composition, characterized in that: 2. The composition according to claim 1, wherein the thermotropic liquid crystal polymer is a wholly aromatic polyester. 3. The composition according to claim 1, wherein the glassy carbon is obtained by carbonizing a thermosetting resin. 4. The composition according to claim 1, wherein the glassy carbon is a glassy carbon having substantially no peak characteristic of graphite in a spectrum by X-ray diffraction.