JP3083197B2 - Oil-containing polyimide resin composition for sliding materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-containing polyimide resin composition for a sliding material which can be injection-molded .

[0002]

2. Description of the Related Art Polyimides which have been developed so far have many excellent properties, but resins having excellent heat resistance but poor workability, and resins developed for the purpose of improving workability, have high heat resistance. It has advantages and disadvantages in performance such as poor solvent resistance, and has a drawback such as a large dimensional change in the heat treatment process accompanying crystallization. In order to solve these drawbacks, the present applicant has disclosed in Japanese Patent Application Laid-Open Nos. 62-236858 and 62-253655 etc. the formula (1) which is one of the constituent elements of the present invention.

[0003]

Embedded image A polyimide resin having a repeating unit represented by The present inventors have found that a resin composition for a sliding material using the above polyimide resin has excellent sliding properties (Japanese Patent Application Laid-Open Nos. 62-265350 and 63-008455). Gazette). However, at a high sliding speed, that is, at a high sliding speed of 50 m / min or more, the friction characteristics of the resin composition for a sliding material are inferior to that at a low speed (for example, 5 m / min). It was not suitable for the sliding material used. In addition, during molding,
There was also a disadvantage that the releasability from the mold was not significantly improved.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition for a sliding material using a polyimide resin by injection molding.
An object of the present invention is to enable molding, to significantly improve the sliding characteristics at high speed , and to further improve the releasability from a mold during molding.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that oil is mixed with a resin composition comprising a polyimide resin and a cured phenol resin and / or a solid lubricant. By injecting
A resin composition for a sliding material, which is moldable, significantly improves the sliding characteristics under high speed, and further improves the releasability from a mold during molding, has completed the present invention.
However, as the phenol resin cured product, a phenol resin cured product impregnated with oil may be used. That is, the present invention provides: (1) 20 to 70% by weight of a polyimide resin having a repeating unit represented by the formula (1) [Formula 6], 70 to 20% by weight of a cured phenol resin, and 10 to 60% of a solid lubricant. 0.1 to 100 parts by weight of the resin composition containing 0.1% by weight.
Injection molding, characterized by containing 11 parts by weight of lubricating oil
Oil-containing polyimide resin composition for possible sliding material,

[0006]

Embedded image (Wherein, X is 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 an ether group. Y ₁ , Y ₂ , Y ₃ and Y
₄ represents a group selected from the group consisting of hydrogen, an alkyl group having 1 to 11 carbon atoms , an alkoxy group having 1 to 11 carbon atoms , chlorine and bromine, and R ₁ represents a fatty acid having 4 to 9 carbon atoms. Group, monocyclic aliphatic group having 4 to 10 carbon atoms, monocyclic aromatic group, condensed polycyclic aromatic group, non-condensed polycyclic in which aromatic groups are connected to each other directly or by a crosslinking member Represents a tetravalent group selected from the group consisting of aromatic groups. (2) After the cured phenolic resin cures the novolak-type or resol-type phenolic resin, it is pulverized to an average particle size of 5
(1) The oil-containing polyimide-based resin composition for a sliding material according to (1), wherein the particle size is 0 μm or less and 80% or more has a particle size of 150 μm or less. The oil-containing polyimide resin composition for a sliding material according to (1), wherein the methanol solubility of the material is 20% by weight or less, (4) the solid lubricant is a fluororesin, graphite, molybdenum disulfide, tungsten disulfide, The oil-containing polyimide resin composition for a sliding material according to (1), which is at least one member selected from the group consisting of fluorinated graphite, boron nitride, silicon nitride, and lead monoxide; (4) The polyimide resin composition for a sliding material according to (4), which is at least one selected from the group consisting of the following (a) to (f): ₂ CF ₂₎ - in Repetitive represented A tetrafluoroethylene resin (b) in the molecule with a return structural units of the _{formula, - (CF 2 CF 2)} - and wherein - [CF (CF ₃₎ CF _2] - four having the repeating structural unit represented by to hexafluoropropylene copolymer resin (c) in the molecule, wherein - - polytetrafluoroethylene (CF ₂ CF ₂₎ - and wherein - _{[CF (OC m F 2m ++ 1} ) CF 2 ] (in the formula , m is a positive integer tetrafluoroethylene having a repeating structural unit represented by) - the perfluoroalkyl vinyl ether copolymer resin (d) in the molecule, wherein, - (CF ₂ CF ₂₎ - and wherein - ( CH ₂ CH ₂₎ - ethylene copolymer (e) in the molecule, wherein - - repeating structural units tetrafluoroethylene having represented by (CH ₂ CH ₂₎ - and formula, - (CFClCF ₂₎ - A trifluoride salt having a repeating structural unit represented by Ethylene - ethylene copolymer resin (f) in the molecule, wherein, - (CF ₂ CH ₂₎ - vinylidene fluoride resin having a repeating structural unit represented by (6) the lubricating oil, the thermal weight loss measurements, 300 ° C. (1) wherein the weight loss is 10% by weight or less; and (7) R in the formula of the polyimide resin having a repeating structural unit represented by the formula (1). ₁ is at least one selected from the group consisting of the following (a) to (e): (1) an oil-containing polyimide-based resin composition for a sliding material according to (1), Aliphatic group (b) Cyclic aliphatic group having 4 to 10 carbon atoms (c) Monocyclic aromatic group represented by the following formula

[0007]

Embedded image (D) a condensed polycyclic aromatic group represented by the following formula [Formula 8]

[0008]

Embedded image (E) a non-fused polycyclic aromatic group in which an aromatic group represented by the following formula [Chemical formula 9] is connected directly or by a bridging member:

[0009]

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 capable of injection molding according to the present invention is represented by the formula (2) [ Chemical formula 10]

[0011]

Embedded image (Wherein X is as defined above) and an ether diamine represented by the formula (3):

[0012]

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.
A polyimide having a repeating structural unit represented by the formula (1) can be obtained by heat dehydration at 00 ° C. or chemical imidization using a commonly used imidizing agent. Also,
Polyimide can also be obtained by simultaneously performing the polyamic acid generation and the thermal imidization reaction.

[0013] The ether diamine formula used Te this way odor (2), as X in the formula (2) is an aliphatic group, [4- (3-aminophenoxy) phenyl] methane, 1 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,
1,1,3,3,3-hexafluoropropane,

In the formula, when X is a direct bond,
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,

In the above formula, bis [4- (3-aminophenoxy) phenyl] ketone and bis [4- {4- (4-aminophenoxy) phenoxy}
Phenyl] ketone, wherein X in the formula is -S-
Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-amino Phenoxy) 3
5-dimethoxyphenyl] sulfide, bis [4- (3
-Aminophenoxy) -3,5-dimethoxyphenyl]
Sulfides, X in the formula is the -SO ₂ - ones group, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, wherein X in the formula is bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether,

In the formula, 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 are used alone or in combination 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.

Further, 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 (3), R ₁ in the formula is Ethylenetetracarboxylic dianhydride and butanetetracarboxylic dianhydride which are aliphatic groups; cyclopentanetetracarboxylic 12 anhydride wherein R ₁ in the formula is a cycloaliphatic group; R _{1 in} the formula Are monocyclic aliphatic groups such as pyromellitic dianhydride, 1,2,3
4-benzenetetracarboxylic dianhydride, in which R ₁ is represented by the following formula:

[0019]

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 (3) 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.

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 anhydride, 3,4-biphenyl dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride Product, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4-dicarboxyphenylphenylsulfide anhydride, 1,2-
Naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, 1,9- Those sealed with a dicarboxylic anhydride such as anthracene dicarboxylic anhydride 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 0.60 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. Molding processability is not enough.

The oil-containing polyimide resin composition for a sliding material which can be injection-molded according to the present invention comprises the above-mentioned polyimide containing a cured phenol resin, a solid lubricant and a lubricating oil. The phenolic resin cured product is prepared by adding a known filler as necessary to a novolak-type or resol-type phenolic resin produced by using a formalin-generating compound for phenols, and adding a crosslinking material such as hexamine or the like and heating. , And then pulverized. The production method is described in, for example,
No. 1, No. 58-17114 and others, and commercially available products include Bell Pearl (registered trademark) manufactured by Kanebo.

The cured phenolic resin contained in the composition of the present invention is a heat-infusible granular or powdery resin having an average particle size of 50 μm or less and 80% by weight.
Those having a particle diameter of 150 microns or less are preferred. If the particle size of the phenolic resin cured product is too large, the adhesion of the powder particles to each other during molding becomes insufficient, causing variations in the molded product, and mechanical properties such as abrasion and bending strength of the molded product. It is not preferable because the strength is reduced. Further, the phenolic resin cured product needs to be sufficiently cured. For example, a "solubility in methanol" which is a measure of the degree of curing, that is, about 10 g of a sample is precisely weighed (the weighed weight is W W ₀ ), 100% methanol about 50
After heating under reflux in 0 ml for 30 minutes, the mixture was filtered through a glass filter, the remaining sample of the filter was washed with about 100 ml of methanol on the filter, and the remaining sample of the filter was dried at a temperature of 70 ° C. for 2 hours. (The weight of the precisely weighed is W ₁ ), and the methanol solubility determined by the following equation is methanol solubility (% by weight) = [(W ₀ −W ₁ ) /
W ₀ ] × 100 20% by weight or less, preferably 15% by weight or less. If the methanol solubility exceeds 20% by weight, foaming occurs during molding, and voids and minute cracks may occur in the molded body, which is not preferable. The amounts of these cured phenolic resins are 20 to 70% by weight of the polyimide resin, 70 to 20% by weight of the cured phenolic resin,
It is within the range of the resin composition consisting of 0 to 60% by weight. If the blending amount of the phenolic resin cured product is less than 20 parts by weight, the abrasion resistance effect cannot be obtained, and if it exceeds 70 parts by weight, the melt viscosity of the composition becomes high and not only melt molding cannot be performed,
The coefficient of friction cannot be reduced, which is not preferable as a sliding material.

The solid lubricant contained in the composition of the present invention is selected from the group consisting of fluororesin, graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride, boron nitride, silicon nitride and lead monoxide. At least one of the following. Among them, the following fluorocarbon resins (a) to (f)
Selected from the group consisting of (A) In the molecule, a tetrafluoroethylene resin having a repeating structural unit represented by the formula,-(CF ₂ CF ₂ )-(b) In the molecule, 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 the formula ,
- _{[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) molecules In the formula,-(CF ₂ CF ₂ )-and the formula,
(E) A tetrafluoroethylene-ethylene copolymer resin having a repeating structural unit represented by — (CH ₂ CH ₂ ) — (e) In a molecule, a formula, — (CH ₂ CH ₂ ) — and a formula
- ethylene copolymer resin (f) in the molecule, wherein, - - (CFClCF ₂₎ - trifluorochloroethylene having a repeating structural unit represented by having a repeating structural unit represented by - (CF ₂ CH ₂₎ It is a vinylidene fluoride resin. Any of these fluororesins may be used, but it is preferable to use the fluororesin (a), that is, tetrafluoroethylene resin, in consideration of heat resistance. The amount of the solid lubricant added was 20 to 70% by weight of the polyimide resin, 70 to 20% by weight of the cured phenol resin,
It is within the range of the resin composition consisting of 60% by weight. If the added amount of the solid lubricant is less than 10% by weight, there is no effect of improving the sliding properties.
The screw of the injection molding machine and the raw material, that is, the resin composition, cannot be properly fed into the molding machine and molding cannot be performed. Even if it can be molded, it is not preferable because the inherent mechanical strength of the polyimide resin is reduced.

Further, the oil contained in the resin composition of the present invention improves the sliding characteristics at high speed. The temperature at the time of mixing and molding the various raw materials for preparing the composition of the present invention is from 250 to 400 ° C, preferably from 300 to 400 ° C. Therefore, the oil contained in the resin composition of the present invention is an oil having excellent heat resistance. In the thermal weight loss measurement, the weight loss at 300 ° C. is 10% or less (measurement of temperature rise from room temperature), preferably 8%.
% Oil. For example, silicone oil,
Perfluoropolyether oil, phenyl ether oil and the like. The amount of the lubricating oil added is from
0% by weight and 70-20% by weight of phenol resin cured product
And a resin composition 1 comprising 10 to 60% by weight of a solid lubricant
0.1 to 11 parts by weight with respect to 00 parts by weight. If the amount of the lubricating oil is less than 0.1 part by weight, the friction coefficient at a high speed increases, and the releasability from a mold during molding is not significantly improved. If the amount exceeds 11 parts by weight, the screw of the injection molding machine and the raw material, that is, the resin composition, will slip during molding, and the resin composition will not be able to be fed into the molding machine and molding will not be possible.

The polyimide resin composition for a sliding material capable of being injection-molded according to the present invention contains carbon fiber, glass fiber, optical fiber, ceramic fiber, potassium titanate fiber, metal fiber, and boron fiber, if necessary. Filling of fibrous reinforcement such as silicon carbide fiber, asbestos, rock wool, calcium carbonate, mica, glass beads, graphite, molybdenum disulfide, clay, silica, alumina, talc, diatomaceous earth, hydrated alumina, shirasu balloon, etc. Agents, stabilizers, colorants, crystal nucleating agents, other thermoplastic resins (eg, polyphenylene sulfide, polyetherimide, polyether sulfone, polyether ketone, liquid crystal polymer, etc.), thermosetting resins (eg, Epoxy resin,
Silicone resin, polyamide imide resin, etc.).

The means for mixing the various raw materials for preparing the polyimide resin composition for a sliding material capable of being injection-molded according to the present invention is not particularly limited, and the raw materials are individually supplied to a melt mixer. Alternatively, two or more kinds may be simultaneously mixed in advance using a general-purpose mixer such as a Henschel mixer, a ball mixer, and a ribbon blender. That is, a phenol resin cured product which has been impregnated with a lubricating oil in advance may be used. Typically, the mixing temperature is 250
To 420 ° C, preferably 300 to 400 ° C. or,
If the oil, which is a raw material of the resin composition, is greatly decomposed during mixing, the generated gas may be removed from the vent port. The molding method of the polyimide resin composition for a sliding material of the present invention can also be applied to compression molding, sinter molding and the like, but it is also possible to form a homogeneous molten blend to form a highly productive injection molding or extrusion molding. Molding can be performed. Further, the present resin composition has excellent sliding characteristics at high speeds in both dry air and oil atmospheres.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The phenol resin cured product, solid lubricant and lubricating oil used in the examples and comparative examples are as follows. (1) Cured phenolic resin Bellpearl C-2000 manufactured by Kanebo Co. This has an average particle size of 22 microns and a methanol solubility of 0.1.
1% by weight or less. (2) Solid lubricant (a) PTFE L-181 manufactured by ICI Asahi Fluoro Co., Ltd. (b) Graphite ACP manufactured by Nippon Graphite Co., Ltd. (c) Lead monoxide Lisage S No. S manufactured by Shinagawa Kako Co., Ltd. (3) Lubricating oil (a) Toshiba Silicone Silicone oil YF-
33-100 Silicone oil 458-100 (b) Phenyl ether oil manufactured by Matsumura Sekiyu KK Moresco Hilube LB-100

[0029]

【Example】

Examples 1 to 9 and Comparative Examples 1 to 7 A polyimide having logarithmic viscosity of 0.46 dl / g obtained from 4,4'-bis (3-aminophenoxy) biphenyl and pyromellitic dianhydride as raw materials and various raw materials were used. After dry mixing at the ratios shown in Table 1, the mixture was extruded at 350 to 400 ° C. using a twin-screw extruder and granulated, and the obtained pellets were injected into an injection molding machine (cylinder temperature 360 to 400 ° C., injection pressure). 900 kg / cm ² , a mold temperature of 180 ° C.), and a test piece specified in each test method described later was formed, and the tensile strength, the coefficient of friction, and the coefficient of wear were measured. The releasability was measured by the following method. Each test method is shown below. In Examples 1, 3, 5, 6 and Comparative Example 3, YF-33-100 was used as the silicone oil in Example 7.
-11-100 and Comparative Example 5 used 458-100. 1) Tensile strength: Measured according to ASTM D-638. 2) Coefficient of friction Using a thrust-type friction and wear tester, surface pressure 3 kg / c
m ² , sliding speed 12m and 110m per minute, mating material sus
45c, the friction coefficient at the time of 2 hours of operation is determined. 3) Wear coefficient Using a cylindrical abrasion tester, the wear coefficient is determined from the wear test results when the surface pressure is kg / cm ² , the sliding speed is 120 m / min, the mating material is sus45c, and the operation time is 72 hours. 4) Using the pellets obtained by the twin-screw extruder, a square container having an outer dimension of 50 mm x 50 mm was molded by an injection molding machine (cylinder temperature: 350 to 400 ° C). that time,
The minimum injection pressure required to obtain a molded article was determined, and the mold release resistance of the molded container was detected by installing a strain gauge on the ejector pin.

Comparison between Tables 1 and 2 shows that the resin composition of the present invention has excellent sliding characteristics (dynamic friction coefficient and wear coefficient) at high speeds and also has improved mold releasability from a mold. You can see that. For sliding members under high speed, the dynamic friction coefficient μ is μ ≦
0.20, wear coefficient K is K ≦ 10 (10 ^-8 cm ³ min / kgmHr)
It is preferable that the resin composition under high speed (V = 1
10 to 120 m / min), the dynamic friction coefficient μ is μ ≦
0.20, wear coefficient K is K ≦ 10 (10 ^-8 cm ³ min / kgmHr)
It is clear from Table 1 that the above condition is satisfied. Furthermore, it is clear that any of Comparative Examples 1 to 7 in Table 2 (Table 3) is inferior to Examples in view of mechanical strength and release resistance.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

EFFECT OF THE INVENTION The oil-containing polyimide resin composition for a sliding material which can be injection-molded according to the present invention has excellent sliding characteristics at high speed without significantly impairing the characteristics of the polyimide resin. Sheets, films, rods, fibers, rods and other molded products of the oil-containing polyimide resin composition for sliding materials of the present invention are used in electrical and electronic equipment, aviation and space equipment, automobile equipment, office equipment, general industry The present invention can be said to be extremely large because it can be widely used for sliding parts at high speed (under dry air and in oil) of equipment and other various equipment. Preparation of polyimide resin composition for sliding material of the present invention
Of course, compression molding, sintering, etc. can be applied to the molding method.
The theory is that a homogeneous melt blend is formed and the productivity is high.
Injection molding or extrusion molding can be performed. Also,
The resin composition can be used under dry air or oil.
Excellent sliding characteristics at high speed even in the atmosphere of
It is.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 61/06 C08L 61/06 C10M 107/00 C10M 107/00 (56) References JP-A-63-314274 (JP, A) 2-191672 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 79/08 C08K 3/00 C08K 5/06 C08L 27/12 C08L 61/06 C10M 107/00 CA ( STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1 to 20% by weight of a polyimide resin having a repeating unit represented by the formula (1), 70 to 20% by weight of a cured phenol resin, and a solid lubricant 10
To 100 parts by weight of a resin composition containing 60% by weight,
An oil-containing polyimide resin composition for an injection-moldable sliding material , comprising 0.1 to 11 parts by weight of a lubricating oil. Embedded image (Wherein, X is 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 an ether group. Y ₁ , Y ₂ , Y ₃ and Y
₄ represents a group selected from the group consisting of hydrogen, an alkyl group having 1 to 11 carbon atoms , an alkoxy group having 1 to 11 carbon atoms , chlorine and bromine, and R ₁ represents a fatty acid having 4 to 9 carbon atoms. Group, monocyclic aliphatic group having 4 to 10 carbon atoms, monocyclic aromatic group, condensed polycyclic aromatic group, non-condensed polycyclic in which aromatic groups are connected to each other directly or by a crosslinking member Represents a tetravalent group selected from the group consisting of aromatic groups. ) 2. The sliding material according to claim 1, wherein the cured phenolic resin is obtained by curing a novolak-type or resol-type phenolic resin and then pulverizing the resin to have an average particle diameter of 50 μm or less and 80% or more of 150 μm or less. Oil-containing polyimide resin composition for use. 3. The oil-containing polyimide resin composition for a sliding material according to claim 1, wherein the cured phenolic resin has a methanol solubility of 20% by weight or less as a scale for indicating the degree of curing. 4. The solid lubricant is at least one selected from the group consisting of fluororesin, graphite, molybdenum disulfide, tungsten disulfide, graphite fluoride, boron nitride, silicon nitride, and lead monoxide. Item 4. The oil-containing polyimide resin composition for a sliding material according to Item 1. 5. The polyimide resin composition for a sliding material according to claim 4, 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 6. The method according to claim 6, wherein the lubricating oil has 3
The oil-containing polyimide resin composition for a sliding material according to claim 1, wherein the weight loss at 00 ° C is 10% by weight or less. 7. The polyimide resin having a repeating structural unit represented by the formula (1), wherein R _{1 in} the formula represents the following (a) to
The oil-containing 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 [Formula 2] (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 4] is connected directly or by a bridging member: