JPH044295A - Sliding resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition containing each specific thermotropic liquid crystal, globular glass-like carbon and fluororesin at specific ratios and usable also in sliding position under severe conditions of high speed and load, especially using a metal as opposite material. CONSTITUTION:The aimed composition containing (A) 87-40 wt.% (preferably 77-55 wt.%) thermotropic liquid crystal polymer which is a (co)polymer (prefer ably wholly aromatic polyester) containing at least a monomer unit expressed by the formula, (B) 10-50 wt.% (preferably 20-40 wt.%) globular glass-like carbon obtained by carbonizing a thermosetting resin at >= 420 deg.C (preferably >= 550 deg.C) and (C) 3-20 wt.% (preferably 3-15wt.%) fluororesin, preferably of polytetrafluoroethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition having excellent sliding properties. In particular, the present invention relates to a sliding resin composition that can be used under harsh conditions, such as when the mating material is metal and it is also used in sliding parts that are subjected to high speed and high loads (of course, the temperature becomes high due to frictional heat).

[Conventional technology] In recent years, synthetic resin products have come into widespread use as machine parts in order to reduce the weight of machines and reduce product costs.Synthetic resin products are also often used for parts that require sliding properties. There is.

Conventionally, resin compositions with good sliding properties are made by adding additives such as solid lubricants and lubricating oils to resins such as polyamide, polyacetal, polyphenylene sulfide, and polytetrafluoroethylene to improve sliding properties. things have been used.

These can be used without any problems at relatively low loads and low speeds, but as the loads and high speeds increase, they tend to wear out more easily, and they also seize or melt due to frictional heat, making them unusable. . For this reason, glass fibers, carbon fibers, various whiskers, etc. are added to improve wear resistance and heat resistance, but these fillers wear out the metals and resins used in the sliding parts. There is a problem with this.

In other words, the sliding properties required for high-load, high-speed sliding parts are wear resistance, heat resistance, and other physical properties rather than friction coefficients. Materials must be selected from a completely different perspective than components.

On the other hand, thermotropic liquid crystal polymers with high melting points have the highest heat resistance among many plastics, so they are less likely to seize or melt due to frictional heat.

However, the mating material of the sliding part is usually made of a metal material such as aluminum alloy or steel, or the thermotropic liquid crystal polymer itself has inferior wear resistance to these metals. There were no examples of it being used for sliding materials.

[Invention or Problems to be Solved] The purpose of the present invention is to solve the problems of the above-mentioned prior art. An object of the present invention is to provide a slidable resin composition.

[Means for Solving the Problems] The slidable resin composition of the present invention contains 87 to 40% by weight of a thermotropic liquid crystal polymer (a) which is a (co)polymer containing at least a monomer unit represented by the following formula. , and 10 to 50% by weight of spherical glass-like carbon (b) obtained by carbonizing a thermosetting resin at a temperature of 420°C or higher, and 3 to 20% by weight of fluororesin (c) (a, b, and C). The total amount is 100% by weight).

-Mathematical formula The details of the present invention will be described below.

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 when melted has a property in which the polymer molecular chains are regularly arranged in parallel in the melted state.

Optical properties The nature of the molten phase can be confirmed by conventional polarization testing using crossed polarizers.

Thermotropic liquid crystal polymers are generally elongated, flat, and made of monomers that have multiple chain extension bonds in either coaxial or parallel relationships that are highly rigid along the long chains of the molecules. be done.

The thermotropic liquid crystal polymer used in the present invention includes a thermoplastic resin in which a part of one polymer chain is composed of a polymer segment that forms an anisotropic melt phase, and the remaining part is a thermoplastic resin that does not form an anisotropic melt phase. Also included are polymers composed of segments.

Also included are composites of multiple thermotropic liquid crystal polymers.

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

Among the above (co)polymers, fully aromatic polyesters containing oxybenzoyl groups are more preferred.

The components of the wholly aromatic polyester that forms the optically anisotropic melt phase as described above include (A) at least one of aromatic dicarboxylic acids and alicyclic dicarboxylic acid compounds, and (B) aromatic hydroxycarboxylic acid. (C) at least one of aromatic diols, alicyclic diols, and aliphatic diol compounds; (D) aromatic dithiols, aromatic thiophenols, and aromatic thiol carboxylic acid compounds; At least one type of (E) aromatic droxamine, aromatic diamine type compound, etc. can be mentioned. These may be composed alone, but most are (A) and (C), (A>
and (D>, (A) (B) and (C), (A>(B) and (E
), or a combination such as (A>(B), (C) and (E), etc.).

Examples of the aromatic dicarboxylic acid compound (A1) include terephthalic acid, 4,4'-diphenyldicarboxylic acid, 4.
4'-triphenyldicarboxylic acid, 2.6-naphthalenedicarboxylic acid, 1.4-naphthalenedicarboxylic acid, 2,
7-naphthalene dicarboxylic acid, diphenyl ether 4.
4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, isophthalic acid, diphenyl ether 3,3'-dicarboxylic acid acids, aromatic dicarboxylic acids such as diphenoxyethane-3,3'-dicarboxylic acid, diphenylethane-3,3'-dicarboxylic acid, 1,6-naphthalene dicarboxylic acid or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, Examples include alkyl, alkoxy or halogen substituted products of the above aromatic dicarboxylic acids, such as methyl terephthalic acid, dimethyl terephthalic acid, ethyl terephthalic acid, methoxyterephthalic acid, and ethoxyterephthalic acid.

(A2) As the alicyclic dicarboxylic acid, trans-14
-Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, or trans-1,4
-(2-methyl)cyclohexanedicarboxylic acid, trans-1,4-(2-chloro)cyclohexanedicarboxylic acid, and alkyl, alkoxy or halogen substituted products of the above alicyclic dicarboxylic acids.

(B) As the aromatic hydroxycarboxylic acid compound,
4-Droxybenzoic acid, 3-Droxybenzoic acid, 6
-Droxy-2-naphthoic acid, 6-Droxy-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-droxybenzoic acid, 3,5-dimethoxy-4-droxybenzoic acid, 6
-Droxy-5-methyl-2-naphthoic acid, 6-Droxy-5-methoxy-2-naphthoic acid, 2-chloro-
4-Hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-droxybenzoic acid, 3,5-dichloro-4-droxybenzoic acid, 2.5
-dichloro-4-droxybenzoic acid, 3-bromo-4
-doxybenzoic acid, 6-doxy5-chloro2-
Examples include alkyl, alkoxy or halogen-substituted aromatic hydroxycarboxylic acids such as naphthoic acid, 6-droxy-7-chloro-2-naphthoic acid, and 6-droxy-5,7-dichloro-2-naphthoic acid. .

(C1) Aromatic diols include 4.4' dihydroxydiphenyl, 3.3'-dihydroxydiphenyl, 4
．． 4'-dihydroxytriphenyl, hydroquinone,
Resorcinol, 2,6-naphthalenediol, 4,4'-
Aromas such as dihydroxydiphenyl ether, bis(4-hydroxyphenoxy)ethane, 3,3'-dihydroxydiphenyl ether, 1,6-naphthalenediol, 2,2bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, etc. Examples include alkyl, alkoxy or halogen-substituted diols of the group diols or aromatic diols such as chlorohydroquinone, methylhydroquinone, t-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, and 4-methylresorcinol.

(C2) Alicyclic diols include trans-14-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexane dimetatool, cis-1,4-cyclohexane dimetatool, trans-1 ,3cyclohexanediol, cis-1,2-
Alicyclic diols such as cyclohexanediol, trans-1,3-cyclohexane dimetatool or trans-1,4-(2-methyl)cyclohexanediol, trans-1,4-(2-chloro)cyclohexanediol Examples include alkyl, alkoxy or halogen-substituted alicyclic diols.

(C3) Alicyclic diols include linear or branched aliphatic diols such as ethylene glycol, 1.3-propanediol, 1.4-butanediol, and neopentyl glycol.

(Dl) As the aromatic dithiol, benzene 1.4-
dithiol, benzene-1,3-dithiol, 2,6-
Examples include naphthalene-dithiol and 2°7-naphthalene-dithiol.

(D2) Aromatic thiophenols include 4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol, and the like.

(D3) Aromatic thiol carboxylic acids include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, 7-mercapto-2-naphthoic acid, and the like.

(E) Aromatic droxamine and aromatic diamine compounds include 4-aminophenol, N-methyl-4-
Aminophenol, 1,4-phenylenediamine, N-
Methyl-1,4-7-enylenediamine, 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
'-Hydroxydiphenyl sulfide, 4.4'-diaminophenyl sulfide (thiodianiline), 4.4
'Diamino diphenyl sulfone, 2.5-diaminotoluene, 4.4 ethylene dianiline, 4.4'-diaminodiphenoxyethane, 4.4'-diaminodiphenylmethane (methylene dianiline), 4.4'-diaminodiphenyl ether (oxydianiline) and the like.

Note that the wholly aromatic polyester generally refers to a polyester substantially obtained from an aromatic carboxylic acid and an aromatic alcohol, but the wholly aromatic polyester of the present invention includes segments that do not form the above-mentioned anisotropic melt phase. Moieties comprised of esters of aliphatic or cycloaliphatic acids or alcohols are also included. Additionally, in the polyester itself or in segments forming an anisotropic melt phase,
Those consisting of esters with aliphatic or alicyclic acids or alcohols are also included as long as they form an anisotropic melt phase.

Specific examples of wholly aromatic polyesters include.

The proportion of the thermotropic liquid crystal polymer in the composition of the present invention is 87 to 40% by weight, preferably 77 to 55% by weight. When the thermotropic liquid crystal polymer exceeds 87% by weight, the abrasion resistance is insufficient, and when it is less than 40% by weight, the strength of the molded article obtained is insufficient.

Furthermore, the glassy carbon in the present invention has a basic structure of a turbostratic structure with an extremely small crystal size, and has a non-oriented structure as a fine M-woven structure, such as phenolic resin, furan resin, epoxy resin, etc. It is manufactured by carbonizing thermosetting resins such as resins, unsaturated polyester resins, urea resins, melamine resins, alkyd resins, and xylene resins at high temperatures.

This glass-like carbon is characterized by its fractured surface having a glass-like luster, and is also characterized by the fact that its fractured surface has a glass-like luster.
Diffraction angle (2θ) of spectrum in line diffraction method 23~2
This is also confirmed by the fact that it has a broad peak around 5 degrees. In addition, the X-ray diffraction method follows the usual method and α-rays (
double line).

Conventional carbon materials such as graphite do not have such a broad peak, but exhibit a sharp d002 peak due to crystallinity at other diffraction angles (2θ-26, 4°).

The glassy carbon of the present invention is preferably one that does not substantially have peaks characteristic of graphite. Moreover, a carbonized product of a mere organic substance does not have a glass-like luster on its fractured surface, and of course does not have a specific diffraction angle peak characteristic of graphite as well as the glassy carbon in its X-ray diffraction spectrum.

In the present invention, 420°C or higher, preferably 550°C
Spherical glassy carbon carbonized at the above temperature is used.

If carbonized at a temperature below 420°C, uncarbonized resin tends to remain, and during heating to melt and mix the high melting point thermotropic liquid crystal polymer, this uncarbonized thermosetting resin will decompose. However, it is not preferable because it has an adverse effect on the composition.

As for the shape of the glassy carbon, it is preferable to have a spherical shape, and it is more preferable that it be close to a true sphere.A non-spherical shape such as an amorphous shape is preferable because it will wear out the metal or resin of the mating material used for the sliding part, for example. do not have.

Further, the amount of spherical glassy carbon added is 10 to 50% by weight, preferably 20 to 40% by weight. Within this range, wear resistance etc. are sufficient and the effects of the present invention can be exhibited.

If the amount of spherical glassy carbon added is less than 10% by weight, the wear resistance will be insufficient, and if it is added in an amount exceeding 50% by weight, no further improvement in wear resistance can be expected, and the molded product This results in a decrease in mechanical strength.

In addition, the fluororesin used in the present invention includes polytetrafluoroethylene (PTFE), PFA which is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, and a copolymer of tetrafluoroethylene and hexafluoropropylene. FEP, EPE which is a copolymer of tetrafluoroethylene, hexafluoropropylene and perfluorovinyl ether, and ET which is a copolymer of ethylene and tetrafluoroethylene.
Examples include FB and modified fluororesins of these fluororesins. Among these, PTFE is particularly preferably used.

The amount of fluororesin added is 3 to 20% by weight, preferably 3 to 15% by weight. If it is less than 3%, there is no effect of preventing wear of the mating material, and if it exceeds 20% by weight, there is no further improvement effect, and the mechanical strength of the molded product is reduced.

Lubricating oil and the like are often used as lubricants in sliding parts, and although these are inert at room temperature, they can unexpectedly exhibit corrosive properties to contact members at high temperatures due to frictional heat. In addition, since compressors are exposed to chemicals such as fluorocarbon gas, resistance to these chemicals is also an issue.

However, the resin composition of the present invention, which is composed of a thermotropic liquid crystal polymer, spherical glass-like carbon, and a fluororesin, has sufficient chemical resistance at high temperatures. It will not be affected by lubricants or other chemicals even under conditions.

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

Additives include inorganic fillers, organic fillers, stabilizers, ultraviolet absorbers, pigments, dyes, modifiers, and the like. Among these, inorganic fillers are particularly important and are often used to improve processability, physical properties, etc.

Inorganic fillers include graphite, molybdenum disulfide, bronze, talc, mica, clay, sericite, calcium carbonate, calcium silicate, calcium phosphate, calcium pyrophosphate, silica, alumina, aluminum hydroxide,
Calcium hydroxide, graphite fluoride, potassium titanate, calcium phosphate, calcium pyrophosphate, etc.
Further, glass fibers, carbon fibers, various whiskers, etc. can also be added to the extent that they do not impair the effects of the present invention.

Furthermore, various thermoplastic and thermosetting resins can be used as the organic filler.

Thermotropic liquid crystal polymer and spherical glassy carbon,
The method of mixing the fluororesin or the above-mentioned additives added thereto is not particularly limited, and various means can be applied.

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

The composition of the present invention thus obtained can be molded by methods such as injection, compression, and extrusion. In the case of compression molding, the compositions of the present invention are triblended into powdered form and molded. Good too.

The composition of the present invention has excellent sliding properties and abrasion resistance, and can be used in shafts and bearings of electrical appliances, office equipment, and power equipment, various gears, cams, bearings, as well as Kiteroll of Deotape and cassette tape, and mechanical parts. Seal end materials, valve seats, links, rod seals, piston rings, rider rings, etc., compressor rotation shafts, etc.
It can be used for rotating sleeves, pistons, impellers, vanes, rotors, rollers, etc.

[Effects of the Invention] The composition of the present invention has the following characteristics and is therefore most suitable as a sliding material for use in high-load, high-speed sliding parts where the mating material is metal.

(1) Since it uses a polymer with a particularly high melting point among conventional plastics, it is less likely to melt or seize due to frictional heat.

(2) Since it uses a specific crow-like carbon, it can be obtained with less wear on the palm, and because it contains fluororesin, it is less likely to damage metal materials such as iron materials such as steel, which are sliding mating members.

(3) In injection molding of the composition of the present invention, since a thermotropic liquid crystal polymer is used, molding is easy because it has a high melting point and good fluidity when melted.

(4) Under the high temperatures caused by the fever, lubricating oil, fluorocarbon gas, etc., which are normally inert, may become corrosive to the parts that come into contact with them. However, since the composition of the present invention is stable against these, it is suitable as a sliding material.

[Examples] The present invention will be explained in more detail with reference to Examples, but these Examples do not limit the scope of the present invention.
This figure shows a preferred embodiment of the present invention.

First, raw materials used in Examples and Comparative Examples are listed below.

■Thermotropic liquid crystal polymer A: Thermotropic liquid crystal polymer (product name: Cyter,
A powder product manufactured by Amoco Performance Products, Inc. in the United States.

Melting point: 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: Cyter, manufactured by Amoco Performance Products, Inc., USA) Powder. Melting point: 350°C9 ■ Spherical glassy carbons A to C are obtained by firing phenolic thermosetting resin as a raw material at the carbonization temperature shown below in a nitrogen atmosphere. It was confirmed that the carbon particle fracture surface clearly has a glassy luster, and the X-ray diffraction spectrum measured with Cu-Ka line (double line) shows a diffraction angle (2θ) of 23
It also had a clearly broad peak around ~25 degrees. In addition, in the glassy carbon particles A and B, the sharp peak characteristic of graphite was not substantially observed;
In the carbon particles, a dooo2 peak of graphite was observed in a Scholter-like manner at a diffraction angle of 2θ=26.4°.

■Fluororesin PT'FE (Daikin Lubron L5 (product name)
(particle size 5 micrometers) Example 1.2 The above raw materials were blended in the proportions shown in Table 1, mixed in a Henschel mixer, and then mixed in a twin screw extruder (manufactured by Ikegai Tekko Co., Ltd.: Model PCM-30). Cylinder temperature for melting and kneading 42
The mixture was granulated into pellets at 0° C. and screw rotation speed 200 rpm).

Next, this pellet is injection molded R (manufactured by Jujuki Kikai Kogyo Co., Ltd.).
Nestal SG 25 type), cylinder temperature 400
°C, injection pressure 1000 ktrf/cd, mold temperature 15
A disc with a diameter of 51 cm and a thickness of 3 cm was molded at 0°C.

The obtained test piece was subjected to a pressure of 6 kg using a Suzuki type tester.
f/all, speed 120m/min, the mating material is a ring-shaped 345C with an outer diameter of 25.6nun and an inner diameter of 20mm! l
The wear coefficient and amount of wear of the mating material were measured using aluminum.

Furthermore, using the injection molding machine described above, a bending test piece was molded under the same conditions, and the obtained test piece was used to perform ASTM D-
790, measure the bending strength.

Example 3.4 The above raw materials were blended in the proportions shown in Table 1, mixed in a Henschel mixer, and then melted and kneaded in a twin screw extruder (Model PCM-30, manufactured by Ikegai Iron Works). temperature 3
50'C, screw rotation speed 20OrDII), and granulated into a pellet shape.

Next, injection mold this beret! (Manufactured by Jujuheiki Kogyo Co., Ltd.:
Nestal SG 25 type), cylinder temperature 340
℃, injection pressure 1000 kgf/cd, mold temperature 80℃
A disk with a diameter of 51 m and a thickness of 3 m was molded under the following conditions, and its wear characteristics were measured in the same manner as in Example 1.2.

Furthermore, using the injection molding machine described above, a bending test piece was molded under the same conditions, and the obtained test piece was used to perform ASTM I)
-790, the bending strength was measured.

Example 5 The above raw materials were blended in the proportions shown in Table 1, mixed in a Henschel mixer, and then melted and kneaded in a twin screw extruder (model PCM-30, manufactured by Ikegai Tekko Co., Ltd.) at a cylinder temperature of 42
The mixture was granulated into pellets at 0° C. and screw rotation speed 20 or D11).

Next, this pellet was heated at a temperature of 420℃ and a pressure of 200kgf/
A test piece with a thickness of 3 mm and a size of 50 x 50 mm was prepared by single-line molding at -, and the wear characteristics were evaluated in the same manner. Also, thickness 3
A flat plate with a size of 1100 x 100 a was prepared, and a test piece with a width of 12.7 m+n and a length of 100 mm was cut out from it, and the bending strength was measured according to ASTM D-790.

Example 6.7 The above raw materials were blended in the proportions shown in Table 1, mixed in a Henschel mixer, and then melted and kneaded in a twin screw extruder (model PCM-30, manufactured by Ikegai Tekko Co., Ltd.) at a cylinder temperature of 42.
The mixture was granulated into pellets at 0° C. and a screw rotation speed of 200 pl'l.

Next, this pellet was heated to a temperature of 360℃ and a pressure of 200+RF.
Compression molded with /-, thickness 3 +n+, size 50 x 50
A test piece was prepared from the city, and its wear characteristics were evaluated in the same manner. Further, a flat plate with a thickness of 31 uI and a size of 100 x 100 was prepared, and a test piece with a width of 12.7 m and a length of 100 fins was cut from it and the bending strength was measured according to ASTM D-790.

The above results are summarized in Table 1.

In addition, 500 cc of the bending test pieces obtained in Examples 1 to 7 were
The mixture was placed in a pressure-resistant container together with 150 L+11 of Suniso 4G oil and sealed, and 500 g of Freon gas S-3 was injected while cooling. This pressure-resistant container was immersed in silicone oil at 165° C. for 48 hours, and after cooling for 4 hours, gas was removed, and the sample was taken out to measure dimensional changes in the length direction and weight changes.

All of the bending test specimens exhibited no dimensional or weight changes, indicating that they had better chemical resistance than the composition made of thermotropic liquid crystal polymer, glass-like carbon, and fluororesin.

Comparative Examples 1 and 2 The raw materials described above were blended in the proportions shown in Table 2, and Example 1.
In the same manner as in 2, pellet granulation, disks, and bending test pieces were formed and evaluated. The results are shown in Table 2.

Comparative Example 3 The raw materials described above were blended in the proportions shown in Table 2, and Example 3.
In the same manner as in 4, perform pellet granulation, form disks, and bend test pieces for evaluation. The results are shown in Table 2.

Comparative Example 4 The above-mentioned raw materials were blended in the proportions shown in Table 2, pelletized and flat plate formed in the same manner as in Example 5, and evaluated. The results are shown in Table 2.

Comparative Examples 5 to 7 The above raw materials were blended in the proportions shown in Table 2, and Example 6,
In the same manner as in Example 7, pellet granulation and flat plate molding were performed and evaluated. The results are shown in Table 2.

Here, in Examples 1 to 7, the proportions of the thermotropic liquid crystal polymer, spherical glassy carbon, and fluororesin are all within desirable ranges, so that both the wear characteristics and the mechanical strength are excellent.

On the other hand, in Comparative Examples 1, 2, and 5.6, the coefficient of friction was increased because the resin composition did not contain fluororesin.
The amount of wear on the mating material has also increased.

The difference is particularly noticeable when the mating material is soft aluminum.

In Comparative Examples 3 and 4, the amount of spherical glassy carbon is less than 10% by weight, so the wear resistance is insufficient.

In Comparative Example 7, the amount of thermotropic liquid crystal polymer was 40
Since it does not exceed % by weight, the mechanical strength is insufficient.

Procedural amendment (formality) August 28, 1990 Commissioner of the Patent Office Toshi Ue Matsu Display of 1 incident 1990 Patent Application No. 105272 2. Name of the invention Sliding resin composition 3 Person who makes corrections Relationship to the case Patent applicant Name Japan Petrochemical Co., Ltd. 4 agents Type engraving of handwritten specification attached to application 7. Contents of amendment

Claims (2)

[Claims] (1) Thermotropic liquid crystal polymer (co)polymer containing at least monomer units represented by the following formula (
a) 87 to 40% by weight, spherical carbon on glass obtained by carbonizing a thermosetting resin at a temperature of 420°C or higher (b) 1
0 to 50% by weight, and 3 to 20% by weight of a fluororesin (c) (the sum of a, b, and c is 100% by weight). General formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) The sliding resin composition according to claim 1, wherein the thermotropic liquid crystal polymer is a wholly aromatic polyester.