CA2071053A1 - Surface coating member - Google Patents
Surface coating memberInfo
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- CA2071053A1 CA2071053A1 CA 2071053 CA2071053A CA2071053A1 CA 2071053 A1 CA2071053 A1 CA 2071053A1 CA 2071053 CA2071053 CA 2071053 CA 2071053 A CA2071053 A CA 2071053A CA 2071053 A1 CA2071053 A1 CA 2071053A1
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- parts
- surface coating
- coating member
- weight
- solid lubricant
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Abstract
TRACT OF THE DISCLOSURE
The present invention concerns a surface coating sliding member made of rubber or plastic applied with a coating of excellent durability and high sliding property, in which the coating contains a solid lubricant such as molybdenum disulfide, a resin matrix and a reinforcement, wherein the resin matrix comprises a fluoro-olefin vinyl ether polymer resin and/or fluoro-olefin vinyl ether vinyl ester copolymer.
The present invention concerns a surface coating sliding member made of rubber or plastic applied with a coating of excellent durability and high sliding property, in which the coating contains a solid lubricant such as molybdenum disulfide, a resin matrix and a reinforcement, wherein the resin matrix comprises a fluoro-olefin vinyl ether polymer resin and/or fluoro-olefin vinyl ether vinyl ester copolymer.
Description
20710~3 SURFACE COATING MEMBER
BACKGROUND OF THE INVENTION
Field of the Invention The present invention concerns a surface coating member and, more in particular, it relates to a surface coating members prepared by applying a lubricating coating to the surface of a rubber or plastic member such as wiper blade, seal packing, O-ring, weather strip, glass run, timing belt, rubber bellows, gear and door catcher. More in particular, the present invention relates to a surface coating member suitable as a surface-coated sliding member such as a wiper blade, glass run, weather strip and O-ring whose surface is in sliding contact with other members.
Description of the Prior Art For a wiper blade rubber, a molding product of natural rubber or synthetic rubber has been employed so far.
However, the wiper rubber of this kind has the following drawbacks and hence is not always satisfactory.
That is, slnce an adhering phenomenon occurs between the wiper blade rubber and a glass surface in the damp-drylng state or under cold climate condition, to bring about a so-called "locking phenomenon" in which the wipe~r 20710~3 operation is blocked, or a so-called "trembling phenomenon", that is, self-exciting vibration due to the negative cha-racteristics of the velocity dependency of the frictional coefficient. This leads to problems such as (1) unsatis-factory wiping, (2) abnormal abrasion at the surface of the blade rubber, (3) shortening for the life in each of the connection portions of the wiper system,(4) increase in the consumption power for the operation motor and (5) eyesore and grating due to the trembling phenomenon.
For overcoming such problems, Japanese Patent Laid-Open Sho 55-15873 proposes to coat the rubber surface of a wiper blade with a silicone composition containing molybdenum disulfide.
However, in the wiper blade rubber having such a coating as described in the above-mentioned patent publi-cation, it has been found that the durability of the coating layer becomes poor. The problem also occurs in the weather strip or the glass run.
Further, the following drawbacks are also caused between the metal surface and the rubber material and the coating material not always has a satisfactory property.
That is, in an oil seal or gasoline cap seal, sticking occurs between the rubber and the metal surface to increase torque upon opening and closure. In an O-ring, packing or timing belt, there happens abnormal abrasion, stlck slip 20710~3 r generation of ringing owing to high slidlng resistance between the rubber and the metal surface. Also in rubber bellows, puncture occurs due to the abnormal abrasion.
Further, in a gear or door catcher made o~ polyacetal, nylon resin, etc. abnormal abrasion, ringing or creaking occurs.
For overcoming the ~oregoing problems, although a countermeasure such as coating of grease has been applied, this lacks in durability.
OBJECT AND SUMMARY OF THE INVENTION
The obfect of the present invention is to overcome the foregoing problems and provide a surface coating member having excellent slid$ng property and also high durability o~ the coating layer.
An improved surface coating member was disclosed by the inventors in PCT/JP91/00533 wherein the above-mentioned problems are solved. The present invention has an object to improve surface coating member of PCT/JP91/00533 and enhance strength and hardwearing properties of a surface layer.
The surface coating member according to the present invention comprises a surface coating member in which a coating layer containing a solid lubricant, a resin matrix and rein-forcement i8 formed at the surface, in which the resin matrix comprises a ~luoro-ole~in vinyl ether polymer resln and/or a ~luoro-ole~ln vinyl ether vinyl ester copolymer resin.
There is no particular restriction to rubber or plastic constituting the main body portion o~ the coating member according to the present invention but various kinds of rubber and plastic can be employed. The rubber may be 20710~3 . .
either of natural or synthetic rubber. As an example of the synthetic rubber, there can be mentioned, for instance, styrene butadiene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber (EPM, EPDM), acrylonitrile buta-diene rubber, chloroprene rubber, isobutylene isoprene rubber, alfin rubber, polyether rubber, polysulfide rubber, silicone rubber, acrylic rubber, fluoro rubber, halogenated polyethylene rubber, urethane rubber, ethylene vinyl acetate rubber, high styrene rubber and acrylonitrile isoprene rubber. Among them, EPDM is particularly, preferred.
As the plastic material, either of a thermosetting resin or a thermoplastic resin may be used.
As an example oi the plastic, there can be mentioned, ior instance, ABS resin, ABS blend, acetal resin (homo-polymer), acryl resin, ACS resin, alkyd resin, amino resin, ASA resin, cellulose type resin, chlorlnated polyether, diallyl phthalate resin, epoxy resin, ethylene - vinyl acetate copolymer, fluoro resin, ionomer, methyl pentene polymer, phenol resin, polyamide (nylon), polyallyl ether, polyallyl sulfone, polybutene-l, polycarbonate, unsaturated polyester resin, polyethylene, polyethylene terephthalate (tetron), polyimide, polyamideimide, polyphenylene oxide, polyphenylene suliide, polypropylene, polystyrene, poly-sulione, polyether sulfone, polyurethane, vinyl chloride ~sin, polyallylate and so on.
The coating layer coating the rubber or plastic comprises a solid lubricant, a resin matrix and reinforcement.
As the resin matrix, a fluoro-olefin vinyl ether polymer resin and/or a fluoro-olefin vinyl ether vinyl ester copolymer resin may be used.
As the solid lubricant, there can be used, for example, sulfide such as molybdenum disulfide and tungsten disulfide, ~luoride such as polytetrafluoro ethylene and fluorinated graphite, graphite and silicone powder. The solid lubricant described above may be used alone or as a combination o~ two or more o~ them. In the present invention, combined use of the sulfide, fluoro compound and graphite is preferred in view of the excellent lubrication resistance, fitness and feeling. In this case, the blending ratio for the sulfide, fluoro compound and graphite is preferably from 10 to 1500 parts by weight o~ the sulfide and 100 to 3000 parts by weight o~ the fluoro compound based on 100 parts by weight of the graphite, more preferably, from 10 to 200 parts by weight of the sulfide and 100 to 2000 parts by weight of the fluoro compound.
It is desirable that the solid lubricant has an average grain size of less than 10 pm, preferably, less than 5 ~m.
partlcularly, pre~erablY~ less than 3 pm.
As the reinforcement, there can be used, for example, carbon black and/or fibrous filler. The carbon black rein-forces the coating layer and acts as black pigment. The fibrous filler reduces wear of the solid lubricant such as polytetrafluoroethylene, silicone powder or the like, so 20710~3 that hardwearing properties and strength of the coating layer are enhanced. As the fibrous filler, there can be used carbon fiber, glass fiber, silicon carbide fiber, alumina (aluminium oxide) fiber, potassium titanate fiber and so on.
It is desirable that the fiber has a diameter of 0.3 ~um to 5.0/um and a length of 5 ~m to 100/um.
The blending ratio of the solid lubricant, resin matrix and reinforcement is preferably from 49.9 to 80 parts by weight of the solid lubricant, 50 to 5 parts by weight of the resin matrix and 0.1 to 15 parts by weight of reinfor-cement, more preferably, from 67 to 85 parts by weight of the solid lubricant, 30 to 10 parts by weight of the resin matrix and 3 to 5 parts by weight of reinforcement.
For ~orming the coating on the surface o* the rubber or the plastic in the present invention, the solid lubricant, the resin matrix, reinforcement and a curing agent may be coated being dispersed or dissolved in an organic solvent.
As the curing agent, there can be used, for example, polyisocyanate and melamine resin.
As the organic solvent. methyl ethyl ketone, toluene, xylene, isopropyl alcohol. isobutanol. n-butanol, butyl acetate, MIBK and cellosolve acetate are pre~erred, for example.
As the coating method, various method such as brushing, spraying or dipping may be employed. Prior to the coating.
the surface of the rubber or plastic may be cleaned or a sur~ace treatment may be applied for lmproving the fitness with the resin matrix. For the surface treàtment, a primer treatment can be mentioned.
20710~3 It should be noted that the present invention differs from that of PCT/JP91/00533 in the presence of the reinfor-cement. Namely, the surface coating member of PCT/JP91/00533 is consisted from the solid lubricant and the resin matrix where the lubricant and the matrix are identical entirely to those of the present invention. (Incidentally, in PCT/JP9l/
00533, it is desirable that the surface coating member comprises 50 to 95 parts by weight of the solid lubricant and 50 to 5 parts by weight of the resin matrix, more par-ticularly, 70 to 90 parts by weight of the solid lubricant and 30 to lO parts by weight of the resin matrix.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Fig. l is a schematic side elevational view for illustrating the method of experiment.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present will now be explained with reference to examples and comparative examples.
Compositions shown in the following (Comparative Example l) - (Comparative Example 13)~ as well as (Example l) - (Example 9) were sprayed on the surface of rubber pieces, and the compositions were cured under the curing conditlons (heatlng conditions) shown for each of them, to form a coating layer at a thickness of lO ~m to the surface of each of the rubber pieces. Each rubber piece was cut into a slze of lO mm x 6 mm x 2 mm to prepare a test piece. The coating sur~ace was ~ormed on the lO mm x 6 mm surface of the test piece.
The test plece was mounted to FALEX No. 1 Tester (Faville-Levally Corporation) and the durability of the coatlng layer was examined.
207105~
Fig. 1 is a schematic side elevational view illustra-ting the state of the test, in which a test piece was held to a test piece holder 2 and urged to the outer circumfe-rential surface of a ring 3 of 35 mm diameter under a load of 9.06 kg (20 LBS). The outer circumferential surface of the ring 3 was made of SAE 4620 steel and the surface roughness was 6 - 12 rms. The ring 3 was reciprocally rotated around the axial center as shown by arrows within a rotational range oi 90 at a rate of 100 cycle/min.
The number of cycles at which the frictional coeffi-cient reached 0.2 was measured as a life cycle. In a case where the coating layer was abraded to expose the rubber layer before the frictional coeificient reached 0.2, the number of cycles up to that time was defined as the life cycle.
The life cycle for each of the comparative examples and the the examples is as shown in Table-l and Table-2. The static irictional coefflcient and the dynamic frictional coef-iicient at the surface of the coating layer ior each of the test pleces beiore the slldlng movement with the ring 3 were measured and the results are also shown together in Table-l and Table-2.
From Table-l and Table-2, it-can be seen that the test pieces of Examples 1 - 9 according to the present invention have low friction coefficient and the durability of the coating layer was remarkably high.
It is seen clearly that the reinforcement enhances durability of the coating layer when compound the com-parative examples 5 to 13 and the examples 1 to 9 wherein the reinforcement is comprised in each of the comparative examples 5 to 13 respectively.
2Q71~
The average grain size of the solid lubricant used hereinafter is less than 5 ~m in each o~ the cases.
In the following descriptions, "parts" means "parts by weight".
(Comparative Example 1) (Polyurethane resin) Nipporan 5185 100 parts (manufactured by Nippon Polyurethane Industry co.) (Isocyanate curing agent) Coronate HL 10.0 parts Curing cond~tions: 80C - 30 min.
(Comparative Example 2) (Polyurethane resin) Nipporan 5185 26.0 parts (manuiactured by Nippon Polyurethane Industry co.) (Molybdenum disul~ide) Technical grade30.0 parts (manuiactured by Climax Molybdenum Co.) (Polytetrafluoroethylene) Lubron L-542.0 parts (manuiactured by Daikin Industry Co.) (Graphite) ACP 1000 2.0 parts (manu~actured by Nippon Graphite Industry Co.) (Isocyanate curing agent) Coronste HL2.6 parts Curing conditions: 80C - 30 min.
Comparative Example 3) (corresponding to Example 3 in Japanese Patent Laid-Open Sho 55-15873) KM-765 (Emulsion with 20X silicone content) -45 parts (manuiactured by Juetsu Chemical Co.) C-PM-4F (catalyst, manu~actured by Juetsu Chemlcal Co.) 4.5 parts g 20710~
Molybdenum disulfide (4.5 ~m average grain size) 4.0 parts Water 52.0 parts Curing condition: After leaving at a room temperature for 10 min, a cured layer was obtained at 150C - 10 min (Comparative Example 4) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 100 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Isocyanate curing agent) Barnock DN980 24 parts (msnufactured by Dainippon Ink Chemical Industry Co.) Curing condition: 80C - 10 min.
(Comparative Example 5) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 26 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade 30 parts (manufactured by Climax Molybdenum Co.) (Polytetrailuoro ethylene) Lubron L-5 42 parts (manufactured by Daikln Industry Co.) (Graphlte) ACP 1000 2 parts (manu~actured by Nippon Graphite Industry Co.) (Isocranate curing agent) Barnock DN980 6.2 parts (Dainippon Ink Chemical Industry Co.) Curlng condltlon: 80C - 10 min.
20710~3 (Comparative Example 6) (Fluoro-olefin vinyl ether vinyl ester copolymer~
Fluonate K702 28 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technlcal grade10 parts (manufactured by Climax Molybdenum Co.) (Polytetrafluoro ethylene) Lubron L-560 parts (manufactured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manufactured by Nippon Graphite Industry Co.) (Isocyanate curing agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical Industry Co.) Curing condition: 80C - 10 min.
(Comparative Example 7) (Fluoro-olefin vinyl ether vlnyl ester copolymer) Fluonate K702 28 parts (manufactured by Dainlppon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade47 parts (manu~actured by Climax Molybdenum Co.) (Polytetrai'luoro ethylene) Lubron L-523 parts (manu~actured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manu~actured by Nippon Graphite Industry Co.) 20710~3 (Isocyanate curing agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical Industry Co.) Curing condition: 80C - 10 min.
(Comparative Example 8) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 49 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade39 parts (Polytetrafluoro ethylene) Lubron L-510 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 6.7 parts Curing condition: 80C - 10 min.
(Comparative Example 9) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 49 parts (Molybdenum dlsulflde) Technical grade47 parts (Polytetrafluoro ethylene) Lubron L-52.5 parts (Graphite) ACP 1000 1.5 parts (Isocyanate curlng agent) Barnock DN980 12.0 parts Curing condltlon: 80C - 10 mln.
(Comparative Example lO) (Fluoro-olefln vlnyl ether vlnyl ester copolymer) 20710~3 Fluonate K702 49 parts (Molybdenum disulfide) Technical grade 49 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 12 parts :
Curing condition: 80C - 10 min.
(Comparative Example ll) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 39 parts (Molybdenum disulfide) Technical grade 59 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 9.4 parts Curing condition: 80C - 10 min.
(Comparative Example 12) (Fluoro-olefln vinyl ether vinyl ester copolymer) Fluonate K702 28 parts (Molybdenum disulfide) Technical grade 70 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 6.7 parts Curing condition: 80C - lO min.
(Comparative Example 13) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 20 parts 20710~3 tMolybdenum disulfide) Technical grade 78 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 4.8 parts Curing condition: 80C - 10 min.
(Example 1) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 26 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade 30 parts (manufactured by Climax Molybdenum Co.~
(Polytetrafluoro ethylene) Lubron L-5 37 parts (manu~actured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manuiactured by Nippon Graphite Industry Co.) (Carbon fiber) Kureka chop C5 parts ~manufactured by Kureha Chemical Industries, Ltd.) (Isocyanate curing agent) Barnock DN980 6.2 parts (Dain~ppon Ink Chemical IndustrY Co.) Curlng condition: 80C - 10 min.
(Example 2) (Fluoro-oleiin vinyl ether vinyl ester copolymer) Fluonate K702 28 parts (manu~actured by Dainippon Ink Chemical Industry Co.) (Molybdenum disuliide) Technical grade 5 parts (manuiactured by Climax Molybdenum Co.) fPolytetrafluoro ethylene) Lubron L-5 60 parts (manufactured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manufactured by Nippon Graphite Industry Co.) (Carbon fiber) Kureka chop C 5 parts (manufactured by Kureha Chemical Industries, Ltd.) tIsocyanate curing agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical IndustrY Co.) Curing condition: 80C - 10 min.
(Example 3) (Fluoro-ole~in vlnyl ether vlnyl ester copolymer) Fluonate K702 28 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade44 parts (manu~actured by Clima~ Molybdenum Co.) (Polytetra~luoro ethylene) Lubron L-S23 parts ~manu~actured by Daikin Industry Co.) (Graphlte) ACP 1000 2 parts (manu~actured by Nippon Graphite Industry Co.) (Potassium titanate fiber) Tismo D 3 parts ~manufactured by Ohtsuka Chemical Industries, Ltd.) (Isocyanate curlng agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical Industry Co.) Curlng condltlon: 80C - 10 mln.
(Example 4) tFluoro-ole~in vlnyl ether vinyl ester copolymer) Fluonate ~702 49 parts (manu~actured bY Dalnlppon Ink Chemlcal Industry Co.)
BACKGROUND OF THE INVENTION
Field of the Invention The present invention concerns a surface coating member and, more in particular, it relates to a surface coating members prepared by applying a lubricating coating to the surface of a rubber or plastic member such as wiper blade, seal packing, O-ring, weather strip, glass run, timing belt, rubber bellows, gear and door catcher. More in particular, the present invention relates to a surface coating member suitable as a surface-coated sliding member such as a wiper blade, glass run, weather strip and O-ring whose surface is in sliding contact with other members.
Description of the Prior Art For a wiper blade rubber, a molding product of natural rubber or synthetic rubber has been employed so far.
However, the wiper rubber of this kind has the following drawbacks and hence is not always satisfactory.
That is, slnce an adhering phenomenon occurs between the wiper blade rubber and a glass surface in the damp-drylng state or under cold climate condition, to bring about a so-called "locking phenomenon" in which the wipe~r 20710~3 operation is blocked, or a so-called "trembling phenomenon", that is, self-exciting vibration due to the negative cha-racteristics of the velocity dependency of the frictional coefficient. This leads to problems such as (1) unsatis-factory wiping, (2) abnormal abrasion at the surface of the blade rubber, (3) shortening for the life in each of the connection portions of the wiper system,(4) increase in the consumption power for the operation motor and (5) eyesore and grating due to the trembling phenomenon.
For overcoming such problems, Japanese Patent Laid-Open Sho 55-15873 proposes to coat the rubber surface of a wiper blade with a silicone composition containing molybdenum disulfide.
However, in the wiper blade rubber having such a coating as described in the above-mentioned patent publi-cation, it has been found that the durability of the coating layer becomes poor. The problem also occurs in the weather strip or the glass run.
Further, the following drawbacks are also caused between the metal surface and the rubber material and the coating material not always has a satisfactory property.
That is, in an oil seal or gasoline cap seal, sticking occurs between the rubber and the metal surface to increase torque upon opening and closure. In an O-ring, packing or timing belt, there happens abnormal abrasion, stlck slip 20710~3 r generation of ringing owing to high slidlng resistance between the rubber and the metal surface. Also in rubber bellows, puncture occurs due to the abnormal abrasion.
Further, in a gear or door catcher made o~ polyacetal, nylon resin, etc. abnormal abrasion, ringing or creaking occurs.
For overcoming the ~oregoing problems, although a countermeasure such as coating of grease has been applied, this lacks in durability.
OBJECT AND SUMMARY OF THE INVENTION
The obfect of the present invention is to overcome the foregoing problems and provide a surface coating member having excellent slid$ng property and also high durability o~ the coating layer.
An improved surface coating member was disclosed by the inventors in PCT/JP91/00533 wherein the above-mentioned problems are solved. The present invention has an object to improve surface coating member of PCT/JP91/00533 and enhance strength and hardwearing properties of a surface layer.
The surface coating member according to the present invention comprises a surface coating member in which a coating layer containing a solid lubricant, a resin matrix and rein-forcement i8 formed at the surface, in which the resin matrix comprises a ~luoro-ole~in vinyl ether polymer resln and/or a ~luoro-ole~ln vinyl ether vinyl ester copolymer resin.
There is no particular restriction to rubber or plastic constituting the main body portion o~ the coating member according to the present invention but various kinds of rubber and plastic can be employed. The rubber may be 20710~3 . .
either of natural or synthetic rubber. As an example of the synthetic rubber, there can be mentioned, for instance, styrene butadiene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber (EPM, EPDM), acrylonitrile buta-diene rubber, chloroprene rubber, isobutylene isoprene rubber, alfin rubber, polyether rubber, polysulfide rubber, silicone rubber, acrylic rubber, fluoro rubber, halogenated polyethylene rubber, urethane rubber, ethylene vinyl acetate rubber, high styrene rubber and acrylonitrile isoprene rubber. Among them, EPDM is particularly, preferred.
As the plastic material, either of a thermosetting resin or a thermoplastic resin may be used.
As an example oi the plastic, there can be mentioned, ior instance, ABS resin, ABS blend, acetal resin (homo-polymer), acryl resin, ACS resin, alkyd resin, amino resin, ASA resin, cellulose type resin, chlorlnated polyether, diallyl phthalate resin, epoxy resin, ethylene - vinyl acetate copolymer, fluoro resin, ionomer, methyl pentene polymer, phenol resin, polyamide (nylon), polyallyl ether, polyallyl sulfone, polybutene-l, polycarbonate, unsaturated polyester resin, polyethylene, polyethylene terephthalate (tetron), polyimide, polyamideimide, polyphenylene oxide, polyphenylene suliide, polypropylene, polystyrene, poly-sulione, polyether sulfone, polyurethane, vinyl chloride ~sin, polyallylate and so on.
The coating layer coating the rubber or plastic comprises a solid lubricant, a resin matrix and reinforcement.
As the resin matrix, a fluoro-olefin vinyl ether polymer resin and/or a fluoro-olefin vinyl ether vinyl ester copolymer resin may be used.
As the solid lubricant, there can be used, for example, sulfide such as molybdenum disulfide and tungsten disulfide, ~luoride such as polytetrafluoro ethylene and fluorinated graphite, graphite and silicone powder. The solid lubricant described above may be used alone or as a combination o~ two or more o~ them. In the present invention, combined use of the sulfide, fluoro compound and graphite is preferred in view of the excellent lubrication resistance, fitness and feeling. In this case, the blending ratio for the sulfide, fluoro compound and graphite is preferably from 10 to 1500 parts by weight o~ the sulfide and 100 to 3000 parts by weight o~ the fluoro compound based on 100 parts by weight of the graphite, more preferably, from 10 to 200 parts by weight of the sulfide and 100 to 2000 parts by weight of the fluoro compound.
It is desirable that the solid lubricant has an average grain size of less than 10 pm, preferably, less than 5 ~m.
partlcularly, pre~erablY~ less than 3 pm.
As the reinforcement, there can be used, for example, carbon black and/or fibrous filler. The carbon black rein-forces the coating layer and acts as black pigment. The fibrous filler reduces wear of the solid lubricant such as polytetrafluoroethylene, silicone powder or the like, so 20710~3 that hardwearing properties and strength of the coating layer are enhanced. As the fibrous filler, there can be used carbon fiber, glass fiber, silicon carbide fiber, alumina (aluminium oxide) fiber, potassium titanate fiber and so on.
It is desirable that the fiber has a diameter of 0.3 ~um to 5.0/um and a length of 5 ~m to 100/um.
The blending ratio of the solid lubricant, resin matrix and reinforcement is preferably from 49.9 to 80 parts by weight of the solid lubricant, 50 to 5 parts by weight of the resin matrix and 0.1 to 15 parts by weight of reinfor-cement, more preferably, from 67 to 85 parts by weight of the solid lubricant, 30 to 10 parts by weight of the resin matrix and 3 to 5 parts by weight of reinforcement.
For ~orming the coating on the surface o* the rubber or the plastic in the present invention, the solid lubricant, the resin matrix, reinforcement and a curing agent may be coated being dispersed or dissolved in an organic solvent.
As the curing agent, there can be used, for example, polyisocyanate and melamine resin.
As the organic solvent. methyl ethyl ketone, toluene, xylene, isopropyl alcohol. isobutanol. n-butanol, butyl acetate, MIBK and cellosolve acetate are pre~erred, for example.
As the coating method, various method such as brushing, spraying or dipping may be employed. Prior to the coating.
the surface of the rubber or plastic may be cleaned or a sur~ace treatment may be applied for lmproving the fitness with the resin matrix. For the surface treàtment, a primer treatment can be mentioned.
20710~3 It should be noted that the present invention differs from that of PCT/JP91/00533 in the presence of the reinfor-cement. Namely, the surface coating member of PCT/JP91/00533 is consisted from the solid lubricant and the resin matrix where the lubricant and the matrix are identical entirely to those of the present invention. (Incidentally, in PCT/JP9l/
00533, it is desirable that the surface coating member comprises 50 to 95 parts by weight of the solid lubricant and 50 to 5 parts by weight of the resin matrix, more par-ticularly, 70 to 90 parts by weight of the solid lubricant and 30 to lO parts by weight of the resin matrix.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Fig. l is a schematic side elevational view for illustrating the method of experiment.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present will now be explained with reference to examples and comparative examples.
Compositions shown in the following (Comparative Example l) - (Comparative Example 13)~ as well as (Example l) - (Example 9) were sprayed on the surface of rubber pieces, and the compositions were cured under the curing conditlons (heatlng conditions) shown for each of them, to form a coating layer at a thickness of lO ~m to the surface of each of the rubber pieces. Each rubber piece was cut into a slze of lO mm x 6 mm x 2 mm to prepare a test piece. The coating sur~ace was ~ormed on the lO mm x 6 mm surface of the test piece.
The test plece was mounted to FALEX No. 1 Tester (Faville-Levally Corporation) and the durability of the coatlng layer was examined.
207105~
Fig. 1 is a schematic side elevational view illustra-ting the state of the test, in which a test piece was held to a test piece holder 2 and urged to the outer circumfe-rential surface of a ring 3 of 35 mm diameter under a load of 9.06 kg (20 LBS). The outer circumferential surface of the ring 3 was made of SAE 4620 steel and the surface roughness was 6 - 12 rms. The ring 3 was reciprocally rotated around the axial center as shown by arrows within a rotational range oi 90 at a rate of 100 cycle/min.
The number of cycles at which the frictional coeffi-cient reached 0.2 was measured as a life cycle. In a case where the coating layer was abraded to expose the rubber layer before the frictional coeificient reached 0.2, the number of cycles up to that time was defined as the life cycle.
The life cycle for each of the comparative examples and the the examples is as shown in Table-l and Table-2. The static irictional coefflcient and the dynamic frictional coef-iicient at the surface of the coating layer ior each of the test pleces beiore the slldlng movement with the ring 3 were measured and the results are also shown together in Table-l and Table-2.
From Table-l and Table-2, it-can be seen that the test pieces of Examples 1 - 9 according to the present invention have low friction coefficient and the durability of the coating layer was remarkably high.
It is seen clearly that the reinforcement enhances durability of the coating layer when compound the com-parative examples 5 to 13 and the examples 1 to 9 wherein the reinforcement is comprised in each of the comparative examples 5 to 13 respectively.
2Q71~
The average grain size of the solid lubricant used hereinafter is less than 5 ~m in each o~ the cases.
In the following descriptions, "parts" means "parts by weight".
(Comparative Example 1) (Polyurethane resin) Nipporan 5185 100 parts (manufactured by Nippon Polyurethane Industry co.) (Isocyanate curing agent) Coronate HL 10.0 parts Curing cond~tions: 80C - 30 min.
(Comparative Example 2) (Polyurethane resin) Nipporan 5185 26.0 parts (manuiactured by Nippon Polyurethane Industry co.) (Molybdenum disul~ide) Technical grade30.0 parts (manuiactured by Climax Molybdenum Co.) (Polytetrafluoroethylene) Lubron L-542.0 parts (manuiactured by Daikin Industry Co.) (Graphite) ACP 1000 2.0 parts (manu~actured by Nippon Graphite Industry Co.) (Isocyanate curing agent) Coronste HL2.6 parts Curing conditions: 80C - 30 min.
Comparative Example 3) (corresponding to Example 3 in Japanese Patent Laid-Open Sho 55-15873) KM-765 (Emulsion with 20X silicone content) -45 parts (manuiactured by Juetsu Chemical Co.) C-PM-4F (catalyst, manu~actured by Juetsu Chemlcal Co.) 4.5 parts g 20710~
Molybdenum disulfide (4.5 ~m average grain size) 4.0 parts Water 52.0 parts Curing condition: After leaving at a room temperature for 10 min, a cured layer was obtained at 150C - 10 min (Comparative Example 4) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 100 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Isocyanate curing agent) Barnock DN980 24 parts (msnufactured by Dainippon Ink Chemical Industry Co.) Curing condition: 80C - 10 min.
(Comparative Example 5) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 26 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade 30 parts (manufactured by Climax Molybdenum Co.) (Polytetrailuoro ethylene) Lubron L-5 42 parts (manufactured by Daikln Industry Co.) (Graphlte) ACP 1000 2 parts (manu~actured by Nippon Graphite Industry Co.) (Isocranate curing agent) Barnock DN980 6.2 parts (Dainippon Ink Chemical Industry Co.) Curlng condltlon: 80C - 10 min.
20710~3 (Comparative Example 6) (Fluoro-olefin vinyl ether vinyl ester copolymer~
Fluonate K702 28 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technlcal grade10 parts (manufactured by Climax Molybdenum Co.) (Polytetrafluoro ethylene) Lubron L-560 parts (manufactured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manufactured by Nippon Graphite Industry Co.) (Isocyanate curing agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical Industry Co.) Curing condition: 80C - 10 min.
(Comparative Example 7) (Fluoro-olefin vinyl ether vlnyl ester copolymer) Fluonate K702 28 parts (manufactured by Dainlppon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade47 parts (manu~actured by Climax Molybdenum Co.) (Polytetrai'luoro ethylene) Lubron L-523 parts (manu~actured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manu~actured by Nippon Graphite Industry Co.) 20710~3 (Isocyanate curing agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical Industry Co.) Curing condition: 80C - 10 min.
(Comparative Example 8) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 49 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade39 parts (Polytetrafluoro ethylene) Lubron L-510 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 6.7 parts Curing condition: 80C - 10 min.
(Comparative Example 9) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 49 parts (Molybdenum dlsulflde) Technical grade47 parts (Polytetrafluoro ethylene) Lubron L-52.5 parts (Graphite) ACP 1000 1.5 parts (Isocyanate curlng agent) Barnock DN980 12.0 parts Curing condltlon: 80C - 10 mln.
(Comparative Example lO) (Fluoro-olefln vlnyl ether vlnyl ester copolymer) 20710~3 Fluonate K702 49 parts (Molybdenum disulfide) Technical grade 49 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 12 parts :
Curing condition: 80C - 10 min.
(Comparative Example ll) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 39 parts (Molybdenum disulfide) Technical grade 59 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 9.4 parts Curing condition: 80C - 10 min.
(Comparative Example 12) (Fluoro-olefln vinyl ether vinyl ester copolymer) Fluonate K702 28 parts (Molybdenum disulfide) Technical grade 70 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 6.7 parts Curing condition: 80C - lO min.
(Comparative Example 13) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 20 parts 20710~3 tMolybdenum disulfide) Technical grade 78 parts (Graphite) ACP 1000 2 parts (Isocyanate curing agent) Barnock DN980 4.8 parts Curing condition: 80C - 10 min.
(Example 1) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate K702 26 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade 30 parts (manufactured by Climax Molybdenum Co.~
(Polytetrafluoro ethylene) Lubron L-5 37 parts (manu~actured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manuiactured by Nippon Graphite Industry Co.) (Carbon fiber) Kureka chop C5 parts ~manufactured by Kureha Chemical Industries, Ltd.) (Isocyanate curing agent) Barnock DN980 6.2 parts (Dain~ppon Ink Chemical IndustrY Co.) Curlng condition: 80C - 10 min.
(Example 2) (Fluoro-oleiin vinyl ether vinyl ester copolymer) Fluonate K702 28 parts (manu~actured by Dainippon Ink Chemical Industry Co.) (Molybdenum disuliide) Technical grade 5 parts (manuiactured by Climax Molybdenum Co.) fPolytetrafluoro ethylene) Lubron L-5 60 parts (manufactured by Daikin Industry Co.) (Graphite) ACP 1000 2 parts (manufactured by Nippon Graphite Industry Co.) (Carbon fiber) Kureka chop C 5 parts (manufactured by Kureha Chemical Industries, Ltd.) tIsocyanate curing agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical IndustrY Co.) Curing condition: 80C - 10 min.
(Example 3) (Fluoro-ole~in vlnyl ether vlnyl ester copolymer) Fluonate K702 28 parts (manufactured by Dainippon Ink Chemical Industry Co.) (Molybdenum disulfide) Technical grade44 parts (manu~actured by Clima~ Molybdenum Co.) (Polytetra~luoro ethylene) Lubron L-S23 parts ~manu~actured by Daikin Industry Co.) (Graphlte) ACP 1000 2 parts (manu~actured by Nippon Graphite Industry Co.) (Potassium titanate fiber) Tismo D 3 parts ~manufactured by Ohtsuka Chemical Industries, Ltd.) (Isocyanate curlng agent) Barnock DN980 6.7 parts (Dainippon Ink Chemical Industry Co.) Curlng condltlon: 80C - 10 mln.
(Example 4) tFluoro-ole~in vlnyl ether vinyl ester copolymer) Fluonate ~702 49 parts (manu~actured bY Dalnlppon Ink Chemlcal Industry Co.)
2'Q'71'0~
(Molybdenum disulfide) Technlcal grade 36 parts (Polytetrafluoro ethylene) Lubron L-5 10 parts (Graphite) ACP 1000 2 parts (Potassium titanate fiber) Tismo D3 parts (manufactured by Ohtsuka Chemical Industries, Ltd.) (Isocyanate curing agent) Barnock DN980 6.7 parts Curlng condition: 80C - 10 min.
(Example 5) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate X702 49 parts (Molybdenum disulfide) Technical grade 44 parts (Polytetrafluoro ethylene) Lubron L-5 2.5 parts (Graphite) ACP 1000 1.5 parts (Silicon carbide whisker) TWS-100 3 parts (manufactured by Tokai Carbon Co., Ltd.) (Isocyanate curing agent) Barnock DN980 12.0 parts Curing condition: 80C - 10 min.
(Example 6) (Fluoro-ole~in vinyl ether vinyl ester copolymer) Fluonate K702 49 parts tMolYbdenum disul~ide) Technical grade 46 parts (Graphite) ACP 1000 2 parts (Silicon carbide whisker) TWS-100 3 parts (manufactured by Tokai Carbon Co., Ltd.) . _ .
(Isocyanate curing agent) Barnock DN980 12 parts Curing condition: 80C - 10 min.
(Example 7) 2~71053 (Fluoro-olefin vinyl et~er vinyl ester copolymer) Fluonate K702 39 parts (Molybdenum dlsulfide) Technlcal grade 54 parts (Graphite) ACP 1000 2 parts ~Glass fiber) GP-I-O 5 parts (manufactured by Unitika U.M. Glass Ltd.) (Isocyanate curing agent) Barnock DN980 9.4 parts Curing condition: 80C - 10 min.
(E~ample 8) (Fluoro-olefin vinyl ether vinyl ester copolYmer) Fluonate K702 28 parts (Molybdenum disulfide) Technical grade 6S parts-(Graphite) ACP iooo 2 parts (Potassium titanate fiber) Tismo D 5 parts (manufactured by Ohtsuka Chemical Industries, Ltd.) (Isocyanate curing agent) Barnock DN980 6.7 parts Curing condition: 80C - 10 min.
(Example 9) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate ~702 20 parts (Molybdenum disul~lde) Technlcal grade 73 parts (Graphlte) ACP 1000 2 parts (Carbon fiber) Kureka chop C 5 parts (manufactured by Kureha Chemical Industries, Ltd.) (Isocyanate curlng agent) Barnock DN980 4.8 parts Curing condltion: 80C - 10 min.
?n7~ ~ r?
Table - 1 .
C~ ~ar ~iv- 1 _ 3 4 5 6 7 frictional i. 7 O. 25 0 13 0.23 0.10 0.090.10 f rlctional . . . .
t~ o. 5 0 35 0.13 0.38 0.14 0. l60.15 Endur~nce life tsliding cycles) 10 200 lOOO lOO 45000 42000 44000 Compara t ive 8 9 10 ¦11 12 13 St~tic .. .
co f(f~ci-n) 0.13 0.13 0.14 0 1 0.1 0 09 ~ 0.17 0.17 0.170. lG O. 16 0 14 Enduranc- lif- .
~sliding cycl--33000 35000 3500037000 37000 39000 . .
- 18 - .
20710~
Table--2 ~ e 1--2 3--4 5--6--7 .
frictiono; O. 11 0.10 O. 11 0.14 0;15 0.16 0.11 Dyn~tic coeftic~ent O. 18 O. 17 0.16 0.19 O. 19 O. 19 D 17 Enduranco lifo ~sliding cycles120000 100000 100000 9000O 80000 80000 97000 Example ¦ 8 ¦ 9 Stotlc frictionol O. 11 O 10 Dynotlc frictlonol ccef(fic~ent O. 17 0.15 Enduronc- llfo ~liding cycl-s 96000 96000 As has been described above, the surface coating member according to the present inventlon has an extremely low friction coefficient for the coating surface and the durability of the coating layer is remarkably high.
(Molybdenum disulfide) Technlcal grade 36 parts (Polytetrafluoro ethylene) Lubron L-5 10 parts (Graphite) ACP 1000 2 parts (Potassium titanate fiber) Tismo D3 parts (manufactured by Ohtsuka Chemical Industries, Ltd.) (Isocyanate curing agent) Barnock DN980 6.7 parts Curlng condition: 80C - 10 min.
(Example 5) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate X702 49 parts (Molybdenum disulfide) Technical grade 44 parts (Polytetrafluoro ethylene) Lubron L-5 2.5 parts (Graphite) ACP 1000 1.5 parts (Silicon carbide whisker) TWS-100 3 parts (manufactured by Tokai Carbon Co., Ltd.) (Isocyanate curing agent) Barnock DN980 12.0 parts Curing condition: 80C - 10 min.
(Example 6) (Fluoro-ole~in vinyl ether vinyl ester copolymer) Fluonate K702 49 parts tMolYbdenum disul~ide) Technical grade 46 parts (Graphite) ACP 1000 2 parts (Silicon carbide whisker) TWS-100 3 parts (manufactured by Tokai Carbon Co., Ltd.) . _ .
(Isocyanate curing agent) Barnock DN980 12 parts Curing condition: 80C - 10 min.
(Example 7) 2~71053 (Fluoro-olefin vinyl et~er vinyl ester copolymer) Fluonate K702 39 parts (Molybdenum dlsulfide) Technlcal grade 54 parts (Graphite) ACP 1000 2 parts ~Glass fiber) GP-I-O 5 parts (manufactured by Unitika U.M. Glass Ltd.) (Isocyanate curing agent) Barnock DN980 9.4 parts Curing condition: 80C - 10 min.
(E~ample 8) (Fluoro-olefin vinyl ether vinyl ester copolYmer) Fluonate K702 28 parts (Molybdenum disulfide) Technical grade 6S parts-(Graphite) ACP iooo 2 parts (Potassium titanate fiber) Tismo D 5 parts (manufactured by Ohtsuka Chemical Industries, Ltd.) (Isocyanate curing agent) Barnock DN980 6.7 parts Curing condition: 80C - 10 min.
(Example 9) (Fluoro-olefin vinyl ether vinyl ester copolymer) Fluonate ~702 20 parts (Molybdenum disul~lde) Technlcal grade 73 parts (Graphlte) ACP 1000 2 parts (Carbon fiber) Kureka chop C 5 parts (manufactured by Kureha Chemical Industries, Ltd.) (Isocyanate curlng agent) Barnock DN980 4.8 parts Curing condltion: 80C - 10 min.
?n7~ ~ r?
Table - 1 .
C~ ~ar ~iv- 1 _ 3 4 5 6 7 frictional i. 7 O. 25 0 13 0.23 0.10 0.090.10 f rlctional . . . .
t~ o. 5 0 35 0.13 0.38 0.14 0. l60.15 Endur~nce life tsliding cycles) 10 200 lOOO lOO 45000 42000 44000 Compara t ive 8 9 10 ¦11 12 13 St~tic .. .
co f(f~ci-n) 0.13 0.13 0.14 0 1 0.1 0 09 ~ 0.17 0.17 0.170. lG O. 16 0 14 Enduranc- lif- .
~sliding cycl--33000 35000 3500037000 37000 39000 . .
- 18 - .
20710~
Table--2 ~ e 1--2 3--4 5--6--7 .
frictiono; O. 11 0.10 O. 11 0.14 0;15 0.16 0.11 Dyn~tic coeftic~ent O. 18 O. 17 0.16 0.19 O. 19 O. 19 D 17 Enduranco lifo ~sliding cycles120000 100000 100000 9000O 80000 80000 97000 Example ¦ 8 ¦ 9 Stotlc frictionol O. 11 O 10 Dynotlc frictlonol ccef(fic~ent O. 17 0.15 Enduronc- llfo ~liding cycl-s 96000 96000 As has been described above, the surface coating member according to the present inventlon has an extremely low friction coefficient for the coating surface and the durability of the coating layer is remarkably high.
Claims (15)
1. A surface coating member in which a coating layer containing a solid lubricant, a resin matrix and reinfor-cement is formed at the surface, wherein the resin matrix comprises a fluoro-olefin vinyl ether polymer resin and/or fluoro-olefin vinyl ether vinyl ester copolymer resin.
2. A surface coating member as defined in claim 1, wherein the solid lubricant comprises one or more selected from the group consisting of sulfide, fluoro compound, graphite and silicon powder.
3. A surface coating member as defined in claim 1 or 2, wherein the reinforcement is carbon black.
4. A surface coating member as defined in claim 1 or 2, wherein the reinforcement is fibrous filler.
5. A surface coating member as defined in claim 1, wherein said fibrous filler is one or more selected from the group consisting of carbon fiber, glass fiber, silicon carbide fiber, alumina fiber and potassium titanate fiber.
6. A surface coating member as defined in one of claims 1 to 5, wherein the blending ratio of the solid lubricant, the resin matrix and the reinforcement is from 49.9 to 80 parts by weight of the solid lubricant, 50 to 5 parts by weight of the resin matrix and 0.1 to 15 parts by weight of the reinforcement.
7. A surface coating member as defined in one of claims 1 to 5, wherein the blending ratio of the solid lubricant, the resin matrix and the reinforcement is from 67 to 85 parts by weight of the solid lubricant, 30 to 10 parts by weight of the resin matrix and 3 to 5 parts by weight of the reinforcement.
8. A surface coating member as defined in one of claims 2 to 7, wherein the sulfide is molybdenum disulfide and/or tungsten disulfide.
9. A surface coating member as defined in one of claims 2 to 8, wherein the fluoro compound is polytetrafluoro ethylene and/or fluorinated graphite.
10. A surface coating member as defined in one of claims 2 to 9, wherein the solid lubricant comprises a sulfide, fluoro compound and graphite and the blending ratio is from 10 to 1500 parts by weight of the sulfide and 100 to 3000 parts by weight of the fluoro compound based on 100 parts by weight of graphite.
11. A surface coating member as defined in one of claims 2 to 10, wherein the average grain size of the solid lubri-cant is less than 10µm.
12. A surface coating member as defined in claim 11, wherein the average grain size of the solid lubricant is less than 5 µm.
13. A surface coating member as defined in claim 10, wherein the average grain size of the solid lubricant is less than 3 µm.
14. A surface coating member as defined in one of claims 1 to 13, wherein the surface coating member is a wiper blade rubber.
15. A surface coating member as defined in one of claims 1 to 13, wherein the surface coating member is a seal packing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2071053 CA2071053A1 (en) | 1991-04-22 | 1992-03-27 | Surface coating member |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1991/000533 WO1992018560A1 (en) | 1991-04-22 | 1991-04-22 | Surface-coated member |
| CA 2071053 CA2071053A1 (en) | 1991-04-22 | 1992-03-27 | Surface coating member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2071053A1 true CA2071053A1 (en) | 1993-09-28 |
Family
ID=25675203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2071053 Abandoned CA2071053A1 (en) | 1991-04-22 | 1992-03-27 | Surface coating member |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2071053A1 (en) |
-
1992
- 1992-03-27 CA CA 2071053 patent/CA2071053A1/en not_active Abandoned
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