JP2981301B2 - Polyimide resin composition for sliding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyimide resin composition for a sliding material.

[0002]

2. Description of the Related Art Conventionally, polyimide has extremely excellent heat resistance, mechanical strength, dimensional stability, flame retardancy, electrical insulation, etc., so that electric / electronic equipment, space It is used in fields such as aviation equipment and transportation equipment, and is expected to be used in fields requiring heat resistance in the future. Polyimides exhibiting excellent properties have already been developed.

[0003] However, many of the polyimides developed so far have excellent properties. However, although they have excellent properties, they have poor workability, and resins developed for the purpose of improving the workability have high heat resistance and solvent resistance. There were advantages and disadvantages in performance such as inferior.

[0004] For example, in J. Polym. Sci. Mac
romol, Rev. , 11, 161 (1976) or J.A. Elast. Plast. , 7, 285 (197
Formula (6) described in 5)

[0005]

Embedded image Is a polyimide having a basic skeleton represented by the following formula (manufactured by DuPont; trade name: Kapton, Vespel), which does not have a clear glass transition temperature and is excellent in heat resistance, but is difficult to process when used as a molding material. It must be processed using techniques such as sinter molding. Also,
When used as a material for electrical and electronic parts, dimensional stability,
It has a drawback of high water absorption which has an adverse effect on insulation and solder heat resistance.

In addition, formula (7) [formula 10]

[0007]

Embedded image Is a resin having excellent workability, but has a glass transition temperature of 217.
° C, and is soluble in halogenated hydrocarbons such as methylene chloride, and is not a satisfactory resin in terms of heat resistance and solvent resistance.

In order to solve these drawbacks, the present applicant has disclosed Japanese Patent Application Laid-Open Nos. 62-236858 and 62-25365.
5 and the like, one of the constituent elements of the present invention represented by the formula (1)

[0009]

Embedded image A polyimide resin having a repeating unit represented by

The polyimide resin is used in a wide range of fields because of its excellent properties such as thermal properties and electrical properties. However, the polyimide resin has a high melt viscosity and is still difficult to process. It has drawbacks such as a large dimensional change during the heat treatment process accompanying crystallization and a lack of dimensional stability.

Further, the present inventors have found that it is effective to blend the above-mentioned polyimide resin with a thermotropic liquid crystal polymer in order to improve the disadvantages of the above-mentioned polyimide resin, and have filed a patent application ( Japanese Patent Application Laid-Open No. Hei 4- 17537
3 ). Since this resin composition is excellent in heat resistance, toughness, workability, and the like, application development to a field conventionally considered to be a metal or ceramics area has been promoted. However, these resin compositions are still not sufficiently satisfactory in terms of lubricity and sliding properties.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition comprising a polyimide resin and a thermotropic liquid crystal polymer with excellent heat resistance and workability, as well as excellent sliding properties and mechanical properties. It is in.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a fluororesin and a carbon fiber were added to a resin composition containing a polyimide resin and a thermotropic liquid crystal polymer. It has been found that by blending, it is possible to obtain a high-strength sliding material having excellent sliding properties and mechanical properties, and completed the present invention.

That is, the present invention provides: (1) 50 to 99% by weight of a polyimide resin having a repeating unit represented by the formula (1) [Formula 12] and one or more mixtures of two or more thermotropic liquid crystal polymers. And 1 to 60 parts by weight of a fluororesin, based on 100 parts by weight of the resin composition.
And 5-160 Ri name contains carbon fiber parts by weight, 3
A polyimide resin composition for a sliding material, which is injection-molded in a temperature range of 70 to 410C .

[0015]

Embedded image (Wherein, X is selected from the group consisting of direct bond, sulfur, divalent hydrocarbon group having 1 to 10 carbon atoms, hexafluorinated isopropylidene group, carbonyl group, thio group, sulfonyl group, and heavy element . Y ₁ , Y ₂ , Y ₃ and Y ₄ each represent a group selected from the group consisting of hydrogen, chlorine and bromine, and R ₁ represents an aliphatic group having 4 to 9 carbon atoms and 4 carbon atoms. A group consisting of 10 to 10 monocyclic aliphatic groups, monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups in which the aromatic groups are interconnected directly or by a bridge member 4 selected from
Represents a valence group. )

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image (3) The polyimide resin composition for a sliding material according to (1), wherein the fluororesin is at least one selected from the group consisting of the following (a) to (f): , A tetrafluoroethylene resin having a repeating structural unit represented by-(CF ₂ CF ₂ )-; (b) In a molecule, a compound represented by the formula,-(CF ₂ CF ₂ )-and the formula,-[CF (CF ₃ ) CF _2] - tetrafluoroethylene resin having recurring structural units represented by - the hexafluoropropylene copolymer resin (c) in the molecule, _{wherein, - (CF 2 CF 2)} - and wherein - [CF ( OC _m F _{2m ++ 1} ) CF ₂ ] (wherein m is a positive integer). (D) In the molecule, a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer resin having a repeating structural unit represented by the formula: _{, - (CF 2 CF 2)} - and _{formula, - (CH 2 CH 2)} - Ethylene copolymer resin (e) in the molecule, wherein - - represented by repeated tetrafluoroethylene having a structural unit (CH ₂ CH ₂₎ - and formula, - (CFClCF ₂₎ - in the repeating structural unit represented by (F) Vinylidene fluoride resin having a repeating structural unit represented by the formula,-(CF ₂ CH ₂ )-in the molecule (4) represented by the formula (1) R _{1 in} the formula of the polyimide resin having a repeating structural unit represented by the following (a) to (e)
(1) The polyimide resin composition for a sliding material according to (1), which is at least one member selected from the group consisting of: (a) an aliphatic group having 4 to 9 carbon atoms; and (b) a ring having 4 to 10 carbon atoms. Formula aliphatic group (c) Monocyclic aromatic group represented by the following formula [Formula 17]

[0020]

Embedded image (D) a condensed polycyclic aromatic group represented by the following formula [Formula 18]

[0021]

Embedded image (E) a non-condensed polycyclic aromatic group in which an aromatic group represented by the following formula [Chemical Formula 19] is connected directly or by a crosslinking member:

[0022]

Embedded image It is.

The diamine component used as a raw material of the polyimide resin having a repeating unit represented by the formula (1) as a basic skeleton in the polyimide resin composition for a sliding material of the present invention is represented by the formula (8):

[0024]

Embedded image (Wherein X is as defined above) and an ether diamine represented by the formula (9)

[0025]

Embedded image (Wherein R ₁ is the same as above) with one or more tetracarboxylic dianhydrides in the presence or absence of an organic solvent, and the resulting polyamic acid is chemically or thermally reacted. Can be produced by imidization. The reaction temperature is usually 250 ° C. or lower, the reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. The reaction time varies depending on the type of tetracarboxylic dianhydride used, the type of solvent and the reaction temperature, and the reaction is usually carried out for a time sufficient to complete the production of the intermediate product, polyamic acid. A reaction time of 24 hours, in some cases within 1 hour, is sufficient.

By such a reaction, a polyamic acid corresponding to the repeating unit of the formula (1) is obtained, and the polyamic acid is then dehydrated by heating to 100 to 400 ° C. or chemically dehydrated using a commonly used imidizing agent. By imidization, a polyimide having a repeating structural unit of the formula (1) is obtained. In addition, polyimide can be obtained by simultaneously performing the polyamic acid generation and the thermal imidization reaction.

The ether diamine of the formula (8) used in this method includes a compound represented by the formula (8) wherein X is an aliphatic group, and is represented by [4- (3-aminophenoxy) phenyl].
Methane, 1,1-bis [4- (3-aminophenoxy)
Phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] propane, 2- [4-
(3-aminophenoxy) phenyl] -2- [4- (3
-Aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3
-Methylphenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,
2-bis [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (3-
Aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1
1,3,3,3-hexafluoropropane, in which X is a direct bond, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy)- 3-methylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy)-
3,3'-dichlorobiphenyl, 4,4'-bis (3-
Aminophenoxy) -3,5-dichlorobiphenyl,
4,4′-bis (3-aminophenoxy) -3,3 ′,
5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dibromobiphenyl, 4,4′-bis (3-aminophenoxy) -3,3 ′, 5,5′-tetrabromobiphenyl, wherein X is a —CO— group, and bis [4
-(3-aminophenoxy) phenyl] ketone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] ketone, in which X is a -S- group, and bis [4- (3- Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) 3.5
-Dimethoxyphenyl] sulfide, bis [4- (3-
Aminophenoxy) -3,5-dimethoxyphenyl] sulfide, wherein X is a —SO ₂ — group, and bis [4- (3-aminophenoxy) phenyl] sulfone;
Bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone wherein X is a -O- group, and bis [4- (3-aminophenoxy) phenyl]
Ether, bis [4- (4-aminophenoxy) phenyl] ether, wherein X is other than 1,4
-Bis [4- (3-aminophenoxy) phenoxy] benzene, 1,4-bis [4- (4-aminophenoxy)
Phenoxy] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, bis [4- {4- (4- Aminophenoxy) phenoxy {phenyl] sulfone, etc., and these may be used alone or as a mixture of two or more.

Further, other diamines can be mixed and used as long as the melt fluidity of the thermoplastic polyimide resin is not impaired. Examples of the diamine that can be used as a mixture include m-aminobenzylamine, p-aminobenzylamine, 3,3′-diaminodiphenyl ether,
3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,
3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,
4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy)
Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene,
2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) phenyl] ketone, bis [ 4-aminophenoxy)
Phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone and the like, and these diamines are usually used in a mixture of 30% by weight or less, preferably 5% by weight or less.

As a specific example of tetracarboxylic dianhydride which is one of the raw materials used for producing the polyimide represented by the formula (1), in the formula (9), R ₁ in the formula is Aliphatic groups such as ethylenetetracarboxylic dianhydride and butanetetracarboxylic dianhydride; those in which R ₁ in the formula is a cycloaliphatic group include cyclopentanetetracarboxylic dianhydride; Examples of the group in which ₁ is a monocyclic aliphatic group include pyromellitic dianhydride, 1,2,3
4-benzenetetracarboxylic dianhydride, in which R ₁ is represented by the following formula:

[0030]

Embedded image 3,3 ′, 4,4′- wherein X _{1 in} the formula is a —CO— group
Benzophenonetetracarboxylic dianhydride, 2,2 ',
3,3′-benzophenonetetracarboxylic dianhydride,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride wherein X _{1 in} the formula is a direct bond, 2,2 ′, 3
3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride wherein X ₁ is an aliphatic group, 2,2-bis (2
3-dicarboxyphenyl) propane dianhydride, 1,1
-Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride; Bis (3,4-) wherein X ₁ is an -O- group
Dicarboxyphenyl) ether dianhydride, X in the formula
Bis (3,4-dicarboxyphenyl) sulfone dianhydride in which ₁ is a —SO ₂ — group, and 2,3,6 in which R ₁ in the formula (9) is a condensed polycyclic aromatic group 7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10- Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8
-Phenanthrenetetracarboxylic dianhydride, wherein R _{1 in} the formula is other than bis (3,4 dicarboxy) (p-phenylenedioxy) dianhydride;
These tetracarboxylic dianhydrides are used alone or in combination of two or more. In addition, the polyimide resin represented by the formula (1) used in the present invention includes phthalic anhydride,
2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic Acid anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-
Dicarboxylic anhydrides such as naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, and 1,9-anthracenedicarboxylic anhydride Those sealed with an object can also be used.

The logarithmic viscosity of the polyimide resin having a repeating unit represented by the formula (1) is usually 0.35 to 0.65.
dl / g, preferably in the range of 0.40 to 0.60 dl / g. If the logarithmic viscosity exceeds the above range and is 0.35 or less, mechanical properties and durability become insufficient. If it is 0.65 or more, moldability deteriorates and injection molding becomes difficult. This logarithmic viscosity is 0.5 in a mixed solvent of parachlorophenol / phenol (90/10 weight ratio).
After heating and dissolving with a solvent of g / 100 ml, the solution is cooled to 35 ° C. and measured.

Further, the thermotropic liquid crystal polymer used in the present invention has a thermal structure having at least one basic structure selected from the above formulas (2), (3), (4) and (5). It is a plastic resin.

Representative examples of these thermotropic liquid crystal polymers which are commercially available include Nippon Petrochemical Co., Ltd.
"Zyder" (trademark), Sumitomo Chemical Co., Ltd. "Econol" (trademark), Polyplastics Co., Ltd. "Vectra"
In the polyimide resin composition for a sliding material of the present invention, which is commercially available as (Trademark), the mixing ratio of both the polyimide and the resin composition containing the thermotropic liquid crystal polymer is 50 to 99% by weight of the polyimide resin and the thermoplastic resin. The tropic liquid crystal polymer is 50 to 1% by weight. When the compounding ratio of the thermotropic liquid crystal polymer exceeds 50% by weight, the weld strength of the obtained resin composition decreases and the anisotropy becomes conspicuous. If the amount is less than 1% by weight, the molding processability of the obtained resin composition is not sufficient, and the dimensional stability of the molded product in the heat treatment process accompanying crystallization is not improved.

Further, by blending these thermotropic liquid crystal polymers capable of forming a nematic liquid crystal phase, the crystallization speed is remarkably improved, the crystallization exothermic temperature shifts to a lower temperature side in the temperature increasing process, and the crystallization temperature in the temperature decreasing process. The crystallization exothermic temperature can be shifted to a higher temperature side.

The polyimide resin composition for a sliding material of the present invention contains a fluororesin and carbon fiber as essential components of the above resin composition.

The above-mentioned fluororesin is a synthetic polymer containing a fluorine atom (F) in the molecule, and is generally superior in heat resistance, chemical resistance and electric properties as compared with other synthetic resins. In addition, it has unique low friction characteristics and non-adhesiveness.

Specific examples thereof include: (a) a tetrafluoroethylene resin having a repeating structural unit represented by the formula — (CF ₂ CF ₂ ) — in the molecule; and (b) a formula: — (CF ₂ CF ₂ ) — and a tetrafluoroethylene resin-propylene hexafluoride propylene copolymer resin having a repeating structural unit represented by the formula: — [CF (CF ₃ ) CF ₂ ] —. Tetrafluoride having a repeating structural unit represented by the formula,-(CF ₂ CF ₂ )-and the formula,-[CF (OC _m F _{2m ++ 1} ) CF ₂ ] (where m is a positive integer) (D) tetrafluoride having a repeating structural unit represented by the formula,-(CF ₂ CF ₂ )-and the formula-(CH ₂ CH ₂ )-in the molecule. Ethylene-ethylene copolymer resin, (e) in the molecule, _{, - (CH 2 CH 2)} - and formula, - (CFClCF ₂₎ - trifluorochloroethylene having a repeating structural unit represented by - ethylene copolymer resin, in (f) molecular formula, - (CF ₂ CH ₂₎ - vinylidene fluoride resin having a repeating structural unit represented by, and the like.

Among the above, the ethylene tetrafluoride resin of the formula (a) (hereinafter referred to as PTFE) is excellent in these properties, and is most preferably used in the present invention. The fluororesin used in the polyimide resin composition for a sliding material of the present invention is usually in the form of a powder, and has a particle size of about 1 to 25 microns, preferably about 5 to 10 microns.

The amount of the fluororesin used in the present invention is 1 to 100 parts by weight of the resin composition comprising a polyimide resin and a thermotropic liquid crystal polymer.
It is in the range of 60 parts by weight.

With respect to 100 parts by weight of the resin composition comprising a polyimide resin and a thermotropic liquid crystal polymer,
When the addition amount of the fluororesin is less than 1 part by weight, the effect of improving the friction resistance is small, and when the addition amount exceeds 60 parts by weight, the mechanical properties of the obtained resin composition deteriorate.

The amount of carbon fiber added in the present invention is 5 to 16 carbon fibers per 100 parts by weight of the resin composition comprising a polyimide resin and a thermotropic liquid crystal polymer.
The range is 0 parts by weight.

With respect to 100 parts by weight of the resin composition comprising a polyimide resin and a thermotropic liquid crystal polymer,
If the amount of carbon fiber added is less than 5 parts by weight, the effect of improving mechanical properties is small, and if the amount exceeds 160 parts by weight, the moldability of the obtained resin composition is not sufficient.

The polyimide resin composition for a sliding material according to the present invention may contain, if necessary, glass fiber, optical fiber, ceramic fiber, potassium titanate fiber, metal fiber, boron fiber, silicon carbide fiber, asbestos, and rock. Fibrous reinforcement such as wool, calcium carbonate, mica, glass beads,
Fillers such as graphite, molybdenum disulfide, clay, silica, alumina, talc, diatomaceous earth, hydrated alumina, shirasu balloon, lubricants, mold release agents, stabilizers, coloring agents, crystal nucleating agents, and other thermoplastics Resins (for example, polyphenylene sulfide, polyether imide, polyether sulfone, polyether ketone, etc.) and thermosetting resins (for example, epoxy resin, silicone resin, polyamide imide resin, etc.) may be used in combination.

The means for mixing the various raw materials for preparing the polyimide resin composition for a sliding material of the present invention is not particularly limited, and the raw materials may be individually supplied to a melt mixer. Henschel mixer, ball mixer,
Two or more types may be mixed simultaneously using a general-purpose mixer such as a ribbon blender. Typically, the mixing temperature is 25
The temperature is 0 to 420 ° C, preferably 300 to 400 ° C.

The polyimide resin composition for a sliding material of the present invention can be formed by compression molding, sintering, or the like as a molding method. Molding or extrusion can be performed.

The resin composition of the present invention has excellent sliding properties, heat resistance, chemical resistance, and mechanical strength.
Mechanical parts such as cams, pushing, pulleys, sleeves, bearings, etc., electrical and electronic parts such as connectors, bobbins, IC sockets, impellers, manifolds, valve guides, valve stems, piston skirts, oil pans,
It can be used for automotive parts such as front covers and rocker covers. Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

The thermotropic liquid crystal polymer, fluororesin and carbon fiber used in the examples and comparative examples are as follows. (1) Thermotropic liquid crystal polymer: Xydar SRT-500 manufactured by Nippon Petrochemical Co., Ltd. Econor E-6000 manufactured by Sumitomo Chemical Co., Ltd. Vectra A-950 manufactured by Polyplastics (2) Fluororesin: PTFE L-5 manufactured by Dunkin (3) Carbon fiber: Carbon fiber HTA manufactured by Toho Rayon Co., Ltd.

[0048]

【Example】

Examples 1 to 14 Table 1 shows polyimides having a logarithmic viscosity of 0.46 dl / g and various raw materials obtained from 4,4'-bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride as raw materials. After dry mixing at an appropriate ratio, the mixture is extruded at 370 to 400 ° C. using a twin-screw extruder and granulated, and the obtained pellets are injected into an injection molding machine (cylinder temperature 370 to 410 ° C., injection pressure 900 kg / cm ² , gold (Temperature: 180 ° C.), and a test piece specified by each test method described later was formed, and the friction coefficient, the wear coefficient, the tensile strength, and the bending strength were measured. The results are shown in Tables 1 and 2. In addition, each test method is as follows.

1) Coefficient of friction: Using a thrust-type friction and wear tester, a sliding load of 10 kg / cm ² and a sliding speed of 7 per minute
m, the mating stainless steel 45C, no lubrication, and the friction coefficient at an operation time of 40 minutes are determined. 2) Abrasion coefficient: 5k sliding load using a cylindrical abrasion tester
g / cm ² , sliding speed 100 m / min, mating material SUS30
4. Determine the wear coefficient at 60 hours with no lubrication. 3) Tensile strength: according to ASTM-D-638. 4) Flexural strength: according to ASTM-D790.

Comparative Examples 1 to 5 Except that the mixing ratios of the various raw materials were as shown in Table 2, the same operations as in Example 1 were carried out to produce test pieces, and the properties of the test pieces were measured. The results obtained are shown in Table 3.

Comparing (Tables 1 and 2) with Table 3, Examples 1 to 14 all have excellent sliding characteristics and mechanical properties. On the other hand, it is obvious that Comparative Examples 1 to 5 have disadvantages such as any of these properties being extremely inferior or poor moldability and difficulty in molding.

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

As is apparent from the above description, the molded article made of the polyimide resin composition for a sliding material of the present invention is:
The sliding properties and mechanical properties are extremely excellent without impairing the inherent properties of a resin composition comprising a base resin, a polyimide resin and a thermotropic liquid crystal polymer.

Therefore, since the resin composition of the present invention is very excellent in sliding properties, mechanical properties, heat resistance, and chemical resistance, it can be used in machines such as gears, cams, pushing, pulleys, pulleys, sleeves, bearings and the like. Parts, connectors, bobbins,
It can be widely used for electric and electronic parts such as IC sockets, automobile parts such as impellers, manifolds, valve guides, valve systems, piston skirts, oil pans, front covers, rocker covers, and other various equipment. Therefore, it can be said that the present invention is extremely significant.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshihiko Tsutsumi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside (72) Inventor Toshiaki Takahashi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Hiroyasu Daichi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Mitsui Toatsu Chemicals Co., Ltd. (56) References JP-A-62-185748 (JP, A) JP-A-63-8455 ( JP, A) JP-A-62-253655 (JP, A) JP-A-63-72755 (JP, A)

Claims (4)

(57) [Claims] 1. A composition comprising 50 to 99% by weight of a polyimide resin having a repeating unit represented by the formula (1) [Formula 1] and 50 to 1% by weight of a mixture of one or more thermotropic liquid crystal polymers. The resin composition contains 100 parts by weight of the resin composition, 1 to 60 parts by weight of a fluororesin, and 5 to 160 parts by weight of carbon fibers.
Ri, sliding material for a polyimide resin composition characterized that you injection molding at a temperature in the range of three hundred seventy to four hundred ten ° C.. Embedded image (Wherein X is a group selected from the group consisting of a direct bond, sulfur, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfonyl group, and oxygen. Wherein Y ₁ , Y ₂ , Y ₃ and Y ₄ each represent a group selected from the group consisting of hydrogen, chlorine and bromine, and R ₁ represents an aliphatic group having 4 to 9 carbon atoms;
A group consisting of 10 to 10 monocyclic aliphatic groups, monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups in which the aromatic groups are interconnected directly or by a bridge member Represents a tetravalent group selected from ) 2. The thermotropic liquid crystal polymer has the formula (2) [formula 2], the formula (3) [formula 3], the formula (4) [formula 4]
2. The polyimide resin composition for a sliding material according to claim 1, wherein the polyimide resin composition is at least one member selected from the group consisting of a basic structure having a repeating unit represented by the following formula (5). Embedded image Embedded image Embedded image Embedded image 3. The polyimide resin composition for a sliding material according to claim 1, wherein the fluororesin is at least one selected from the group consisting of the following (a) to (f). (A) In a molecule, a tetrafluoroethylene resin having a repeating structural unit represented by the formula,-(CF ₂ CF ₂ )-; (b) In a molecule, a formula,-(CF ₂ CF ₂ )-and a formula: - [CF (CF ₃₎ CF _2] - tetrafluoroethylene resin having recurring structural units represented by - the hexafluoropropylene copolymer resin (c) in the molecule, _{wherein, - (CF 2 CF 2)} - and wherein - _{[CF (OC m F 2m ++ 1} ) CF 2 ] (wherein, m is a positive integer) tetrafluoroethylene having a repeating structural unit represented by - perfluoroalkyl vinyl ether copolymer resin (d ) In the molecule, a tetrafluoroethylene-ethylene copolymer resin having a repeating structural unit represented by the formula,-(CF ₂ CF ₂ )-and the formula-(CH ₂ CH ₂ )- _{formula, - (CH 2 CH 2)} - and formula, - (C FClCF ₂₎ - trifluorochloroethylene having a repeating structural unit represented by - ethylene copolymer resin (f) in the molecule, _{wherein, - (CF 2 CH 2)} - fluoride having a repeating structural unit represented by Vinylidene resin 4. The polyimide resin having a repeating structural unit represented by the formula (1), wherein R _{1 in} the formula is the following (a) to
The polyimide resin composition for a sliding material according to claim 1, which is at least one member selected from the group consisting of (e). (A) an aliphatic group having 4 to 9 carbon atoms (b) a cyclic aliphatic group having 4 to 10 carbon atoms (c) a monocyclic aromatic group represented by the following formula (6) (D) a condensed polycyclic aromatic group represented by the following formula: (E) a non-condensed polycyclic aromatic group in which an aromatic group represented by the following formula [Chemical formula 8] is connected directly or by a bridging member: