CN101522874A - 固体润滑剂和滑动部件 - Google Patents
固体润滑剂和滑动部件 Download PDFInfo
- Publication number
- CN101522874A CN101522874A CNA2007800384245A CN200780038424A CN101522874A CN 101522874 A CN101522874 A CN 101522874A CN A2007800384245 A CNA2007800384245 A CN A2007800384245A CN 200780038424 A CN200780038424 A CN 200780038424A CN 101522874 A CN101522874 A CN 101522874A
- Authority
- CN
- China
- Prior art keywords
- solid lubricant
- volume
- resin
- acid
- polyvinyl resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000314 lubricant Substances 0.000 title claims abstract description 95
- 239000007787 solid Substances 0.000 title claims abstract description 91
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 23
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 38
- 239000001993 wax Substances 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 11
- 229920000299 Nylon 12 Polymers 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000000344 soap Substances 0.000 claims description 8
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920000571 Nylon 11 Polymers 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical group O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
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- 208000035126 Facies Diseases 0.000 description 28
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- 230000000052 comparative effect Effects 0.000 description 15
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- 238000012360 testing method Methods 0.000 description 12
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- 238000001125 extrusion Methods 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 3
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- 239000004701 medium-density polyethylene Substances 0.000 description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 description 2
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 2
- 229960003132 halothane Drugs 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- PCMORTLOPMLEFB-UHFFFAOYSA-N sinapinic acid Natural products COC1=CC(C=CC(O)=O)=CC(OC)=C1O PCMORTLOPMLEFB-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MXJJJAKXVVAHKI-WRBBJXAJSA-N (9z,29z)-octatriaconta-9,29-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O MXJJJAKXVVAHKI-WRBBJXAJSA-N 0.000 description 1
- YZAZXIUFBCPZGB-FJEDDJBMSA-N (e)-octadec-9-enoic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O.CCCCCCCC\C=C\CCCCCCCC(O)=O YZAZXIUFBCPZGB-FJEDDJBMSA-N 0.000 description 1
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- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
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- ZRKWMRDKSOPRRS-UHFFFAOYSA-N N-Methyl-N-nitrosourea Chemical compound O=NN(C)C(N)=O ZRKWMRDKSOPRRS-UHFFFAOYSA-N 0.000 description 1
- NAKPDBXEVQAMGB-UHFFFAOYSA-N NC(=O)N.N#CC#N.N#CN Chemical compound NC(=O)N.N#CC#N.N#CN NAKPDBXEVQAMGB-UHFFFAOYSA-N 0.000 description 1
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- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000010951 brass Substances 0.000 description 1
- CUWODFFVMXJOKD-UVLQAERKSA-N buserelin Chemical compound CCNC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](COC(C)(C)C)NC(=O)[C@@H](NC(=O)[C@H](CO)NC(=O)[C@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H]1NC(=O)CC1)CC1=CC=C(O)C=C1 CUWODFFVMXJOKD-UVLQAERKSA-N 0.000 description 1
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- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 1
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- IQLUYYHUNSSHIY-HZUMYPAESA-N eicosatetraenoic acid Chemical compound CCCCCCCCCCC\C=C\C=C\C=C\C=C\C(O)=O IQLUYYHUNSSHIY-HZUMYPAESA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 125000005456 glyceride group Chemical group 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
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- C10M169/04—Mixtures of base-materials and additives
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- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
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Abstract
本发明提供一种具有海岛结构的固体润滑剂即通过强化海相使其即使在高负荷条件下使用也不会产生缺损等的问题的固体润滑剂以及埋入有该固体润滑剂的滑动部件。具体而言,本发明提供一种特征为包括:1~10体积%的聚乙烯树脂、20~60体积%的烃类蜡、10~60体积%的三聚氰胺氰脲酸酯、5~15体积%的聚酰胺树脂、2~10体积%的改性聚乙烯树脂的固体润滑剂、以及在滑动部件基体的滑动面形成的孔或槽内埋入所述固体润滑剂而构成的滑动部件。
Description
技术领域
本发明涉及一种固体润滑剂和滑动部件。具体而言,本发明涉及一种即使在高负荷条件下使用也不会产生缺损等的问题的固体润滑剂以及埋入有该固体润滑剂的滑动部件。
背景技术
就埋入在轴承滑动面上形成的孔或槽等而使用的固体润滑剂而言,优选:该固体润滑剂,通过与配合部件(旋转轴等)的滑动容易被导入轴承滑动面,并在那里形成坚固的固体润滑膜,形成的该膜能够长时间经受反复摩擦,而且,膜发生断裂时该膜的自修复性也优良。作为这种固体润滑剂,常用以石墨为主要成分的固体润滑剂。其理由在于:石墨,由于其晶体结构具有层状结构,所以相对于负荷方向呈现较大的阻力,而在相对于滑动方向呈现极小的阻力;而且,石墨具有质软、在从常温至相当高的高温的温度下能够保持润滑性的长处。
但是,以石墨为主要成分的固体润滑剂,由于石墨膜的形成能稍低且被膜的抗反复摩擦的寿命也不够长,所以存在滑动部件(轴承)的使用条件被限制这一问题,例如,难于胜任在高负荷条件下的使用。
作为其它的固体润滑剂,提出有由铅、四氟乙烯树脂、聚烯烃树脂和蜡类构成的固体润滑剂这一技术方案(例如,参照专利文献1)。该固体润滑剂,摩擦系数极低、膜的形成能优良、该膜的寿命也长、膜的自修复性还优良,对于这些对固体润滑剂要求的条件均满足。然而,伴随近年的机械装置的大型化和高性能化,对埋入有固体润滑剂的滑动部件,更进一步地要求负荷能力、摩擦磨耗特性的提高等。
此外,从其它的观点考虑,近年,在材料开发方面具有不可回避地关注环境问题这一动向。作为能够全部满足上述的固体润滑剂的要求的铅成分,由于该铅属于环境负荷物质。因此,存在其使用被限制的问题。
鉴于上述实际情况,本发明的发明人,首先提出了由聚乙烯树脂、烃类蜡和三聚氰胺氰脲酸酯构成的固体润滑剂(例如,参照专利文献2)。该固体润滑剂,是一种成分中不含作为环境负荷物质的铅、并可呈现与含有该铅的固体润滑剂同等或其以上的摩擦磨耗性能的固体润滑剂,使问题得到暂时的解决。然而,通过随后的试验,发现了新的问题。即:该固体润滑剂存在下述的问题。该固体润滑剂,具有由用聚乙烯树脂和烃类蜡形成的海相(连续相)和分散于该海相内的三聚氰胺氰脲酸酯的岛相(分散相)构成的海岛结构。当在滑动部件基体上形成的孔内埋入该固体润滑剂的状态下尝试进行滑动试验时,因在滑动面产生的摩擦热的影响而使该固体润滑剂发生膨胀和软化,在该状态下受到反复摩擦,该固体润滑剂发生塑性流动,作为结果,固体润滑剂的一部分发生缺损。
专利文献1:日本特公昭62-12839号公报
专利文献2:国际公开第WO 2004/046285号公报
发明内容
本发明是基于上述见解而实现的技术方案,其目的在于:提供一种具有海岛结构的固体润滑剂,即强化海相、即使在高负荷条件下使用也不会产生缺损等的问题的固体润滑剂,以及埋入有该固体润滑剂的滑动部件。
本发明的发明人,为了解决上述问题,进行了深入的研讨,结果发现:着眼于具有自润滑性的聚酰胺树脂,针对该聚酰胺树脂和海相,含有增溶剂而提高二者的相溶性,使该聚酰胺树脂与海相结合,谋求强化该海相,由此解决上述问题。
本发明的第一发明点,是一种固体润滑剂,其特征为,包括:1~10体积%的聚乙烯树脂、20~60体积%的烃类蜡、10~60体积%的三聚氰胺氰脲酸酯、5~15体积%的聚酰胺树脂、2~10体积%的改性聚乙烯树脂。
本发明的第二发明点,是一种在滑动部件基体的滑动面形成的孔或槽内埋入上述固体润滑剂而构成的滑动部件。
发明效果
根据本发明,提供一种固体润滑剂以及埋入有该润滑剂的滑动部件,上述固体润滑剂具有由聚乙烯树脂和烃类蜡形成海相,在该海相内分散有三聚氰胺氰脲酸脂的海岛结构,通过作为该海相和聚酰胺树脂的相溶化剂的改性聚乙烯树脂能够提高相溶性,通过聚酰胺与海相结合能够实现该海相的强化提高机械强度,结果能够得到即使在高负荷条件下使用也不会产生缺损等问题,发挥稳定的滑动特定的固体润滑剂。
具体实施方式
以下,详细地说明本发明。本发明的固体润滑剂,优选为在滑动部件基体的滑动面形成的孔或槽等内埋入的固体润滑剂,包括1~10体积%的聚乙烯树脂、20~60体积%的烃类蜡、10~60体积%的三聚氰胺氰脲酸酯、5~15体积%的聚酰胺树脂、2~10体积%的改性聚乙烯树脂。本发明的固体润滑剂,通常具有包括聚乙烯树脂、烃类蜡、聚酰胺树脂和改性聚乙烯树脂的海相和在该海相内分散的三聚氰胺氰脲酸酯的岛相的海岛结构。
在本发明的固体润滑剂中,聚乙烯树脂,发挥作为结合材料的作用形成海相。作为聚乙烯树脂,能够使用低密度聚乙烯树脂(LDPE)、直链低密度聚乙烯树脂(LLDPE)、超低密度聚乙烯树脂(VLDPE)、中密度聚乙烯树脂(MDPE)、高密度聚乙烯树脂(HDPE)、高分子量聚乙烯树脂(HMWPE)、超高分子量聚乙烯树脂(UHMWPE)中的任一种。
作为这些聚乙烯树脂的具体例,可以列举三井化学株式会社制造的“HI-ZEX(商品名):高密度聚乙烯树脂”、“HI-ZEX MILLION(商品名):超高分子量聚乙烯树脂”和“LUBMER(商品名):高分子量聚乙烯树脂”、Hoechst AG制造的“Hostalene(商品名):超高分子量聚乙烯树脂”、住友精化株式会社制造的“Fluothane(商品名):低密度聚乙烯树脂”等。这些聚乙烯树脂,能够单独使用或者作为两种以上的混合物使用。
聚乙烯树脂的配合量,为1~10体积%,优选为3~7体积%。如果配合量不足1体积%,则不能充分发挥作为结合材料的作用,而在超过10体积%配合的情况下,难于获得良好的滑动特性。
在本发明的固体润滑剂中,烃类蜡存在于海岛结构的固体润滑剂,与上述聚乙烯树脂形成海相,主要为固体润滑剂提供低摩擦性。作为烃类蜡,可以列举碳原子数约为24以上的链烷烃类蜡、碳原子数约为26以上的聚乙烯蜡、碳原子数约为28以上的烷基苯、微晶蜡。这些烃类蜡,能够单独使用或作为两种以上的混合物使用。
烃类蜡的配合量为20~60体积%,优选25~45体积%。如果烃类蜡的配合量不足20体积%,则不能获得所期望的低摩擦性,而配合超过60体积%的情况下,不仅使固体润滑剂的强度降低,而且使成型性恶化。
在本发明的固体润滑剂中,三聚氰胺氰脲酸酯,是三聚氰胺与氰尿酸或异氰尿酸的加成化合物。具有六元环结构的三聚氰胺分子和氰尿酸(异氰尿酸)分子借助于氢键而排列为平面状,该平面依靠微弱的结合力叠合为层状,具有类似于二硫化钼或石墨的劈开性。该三聚氰胺氰脲酸酯,分散于海相内而形成岛相,发挥特别是提高耐磨损性、耐负荷性的作用。
三聚氰胺氰脲酸酯的配合量为10~60体积%,优选为20~50体积%。如果配合量不足10体积%,则不能发挥所期望的耐磨损性和耐负荷性的效果,而如果配合超过40体积%,则有可能反而使耐磨损性降低。
在本发明的固体润滑剂中,聚酰胺树脂与下述的作为增溶剂的改性聚乙烯树脂相溶化,形成海相并强化海相,具有提高固体润滑剂的机械强度、耐磨损性的作用。作为聚酰胺树脂,优选聚十二内酰胺(polyLauryllactam)(尼龙-12)和/或聚十一内酰胺(polyundecanamide)(尼龙-11)。
聚酰胺树脂的配合量为5~15体积%,优选为7~12体积%。如果配合量不足5体积%,则未发挥海相的充分强化的效果,而配合超过15体积%,则使耐磨损性降低。
在本发明的固体润滑剂中,改性聚乙烯树脂作为促进形成海相的聚乙烯树脂、烃类蜡与聚酰胺树脂(尼龙-12和尼龙-11)的相溶化的增溶剂发挥作用,具有提高聚乙烯树脂、烃类蜡与聚酰胺树脂(尼龙-12和尼龙-11)的结合力、强化海相的作用。作为改性聚乙烯树脂,优选使接枝单体与聚乙烯树脂接枝聚合而得到的接枝改性聚乙烯树脂。
作为接枝改性聚乙烯树脂中的聚乙烯树脂,能够使用上述的低密度聚乙烯、直链低密度聚乙烯、超低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、高分子量聚乙烯、超高分子量聚乙烯中的任一种。
作为接枝单体,可以列举α,β-不饱和羧酸、α,β-不饱和羧酸酐、α,β-不饱和羧酸衍生物或其两种以上的混合物。作为接枝单体的α,β-不饱和羧酸、其酐或其衍生物,可以列举丙烯酸、甲基丙烯酸、丁烯酸等的一元羧酸、马来酸、富马酸、衣康酸、柠康酸等的二元羧酸、其酐或其盐。其中,优选丙烯酸、甲基丙烯酸、马来酸酐、衣康酸酐以及这些的锌盐和钠盐,特别优选马来酸酐、衣康酸酐。
作为改性聚乙烯树脂的具体例,可以列举三井化学株式会社制造的“ADMER(商品名)”、三菱化学株式会社制造的“MODIC AP(商品名)”等。改性聚乙烯树脂的配合量为2~10体积%,优选为4~7体积%。如配合量不足2体积%,则聚酰胺树脂和形成海相的聚乙烯树脂、烃类蜡等相溶化,不能充分发挥结合它们、强化海相的效果,如果配合超过10体积%,则有可能使海相的滑动特性降低。
上述包括聚乙烯树脂、烃类蜡、三聚氰胺氰脲酸酯、聚酰胺树脂和改性聚乙烯树脂的固体润滑剂,能够以规定量的比例配合作为补加成分的高级脂肪酸、高级脂肪酸酯、高级脂肪酸酰胺、金属皂、磷酸盐和四氟化乙烯树脂。
作为补加成分的高级脂肪酸、高级脂肪酸酯和高级脂肪酸酰胺,形成海相,具有减小摩擦系数、提高成型性的作用。这些补加成分,能够单独使用或者作为两种以上的混合物使用。
高级脂肪酸,优选碳原子数为12以上的饱和或不饱和脂肪酸,具体而言,可以列举十二烷酸、十四烷酸、十六烷酸、十八烷酸、二十烷酸、二十二烷酸、二十六烷酸、二十九烷酸、三十烷酸、十二碳烯酸、十四碳烯酸、油酸(oleic acid)、反油酸(elaidic acid)、亚油酸(linoleicacid)、亚麻酸(linolenic acid)、二十碳四烯酸、二十碳-9-烯酸、芥子酸等。
高级脂肪酸酯,是上述高级脂肪酸和一元醇或多元醇的酯。作为一元醇,可以列举辛醇、十二烷醇、十四烷醇、十六烷醇、十八烷醇、二十二烷醇等。作为多元醇,可以列举乙二醇、丙二醇、丁二醇、丙三醇、季戊四醇、山梨糖醇等。作为高级脂肪酸酯的具体例,可以列举硬脂酸十八醇酯、季戊四醇硬脂酸酯、硬脂酸单甘油酯、山萮酸单甘油酯、褐煤蜡等。
作为高级脂肪酸酰胺的具体例,可以列举月桂酸酰胺、棕榈酸酰胺、肉豆蔻酸酰胺、山萮酸酰胺等的饱和高级脂肪酸酰胺、芥子酸酰胺、油酸酰胺、巴西烯酸酰胺、反油酸酰胺等的不饱和高级脂肪酸酰胺和亚甲基双硬脂酸酰胺、亚乙基双硬脂酸酰胺、亚乙基双油酰胺等的高级脂肪酸双酰胺(也包括高级脂肪酸甲基酰胺、高级脂肪酸乙基酰胺等的饱和或不饱和高级脂肪酸烷基酰胺)。
这些高级脂肪酸、高级脂肪酸酯和高级脂肪酸酰胺的配合量,通常为1~10体积%,优选为3~7体积%。如果配合量不足1体积%,则不能充分发挥所期望的降低耐磨损性和提高成型性的效果,而如果配合超过10体积%,则使成型性降低,并引起固体润滑剂的强度降低。
作为补加成分的金属皂,形成在海相内分散含有的岛相,具有减小摩擦系数、提高热稳定性的作用。该金属皂,是所述的高级脂肪酸和碱金属或碱土金属的盐。具体而言,可以列举硬脂酸锂、硬脂酸钙等。金属皂的配合量通常为3~20体积%,优选为5~15体积%。如果金属皂的配合量不足3体积%,则不能充分发挥降低摩擦系数和提高热稳定性的效果,而配合超过20体积%,会使成型性降低。
作为补加成分的磷酸盐,形成在海相内分散含有的岛相。磷酸盐,虽然其自身并不呈现润滑性,但是能够发挥提高在与配合部件的滑动中在配合部件的表面形成润滑膜的成膜性的效果。作为磷酸盐,可以列举碱金属或碱土金属的磷酸盐、磷酸氢盐、焦磷酸盐、亚磷酸盐或偏磷酸盐。具体而言,可以列举磷酸三锂、磷酸氢二锂、焦磷酸锂、磷酸三钙、磷酸一氢钙、焦磷酸钙、偏磷酸锂、偏磷酸镁、偏磷酸钙等。磷酸盐的配合量通常为3~15体积%,优选为5~10体积%。如果磷酸盐的配合量不足3体积%,则不能充分发挥提高在配合部件的表面形成润滑膜的成膜性的效果,而配合超过15体积%,则润滑膜向配合部件的表面的移动附着量过多,反而使耐磨损性降低。
作为补加成分的四氟化乙烯树脂,作为成型用粉末或细粉主要用于成型,并且,使用通过施加剪切力而纤维状化的高分子量四氟化乙烯树脂(以下,简称为“高分子量PTFE”)。高分子量PTFE,以微细的纤维状分散于海相内,主要具有提供低摩擦性和提高固体润滑剂的韧性的作用。该高分子量PTFE以未烧结形态、或在熔点以上的温度下烧结后以粉碎形态使用。作为高分子量PTFE的具体例,可以列举DUPONT MITSUI FLUOROCHEMICALS制造的“TEFLON(注册商标)7-J”、“TEFLON(注册商标)7A-J”、“TEFLON(注册商标)6-J”、“TEFLON(注册商标)6C-J”等、大金工业株式会社制造的“POLYFLONM-12(商品名)”、“POLYFLON F-201(商品名)”等、Asahi Glass Fluoropolymers制造的“FLUON G163(商品名)”、“FLUON G190(商品名)”、“FLUON CD076(商品名)”、“FLUON CD090(商品名)”等、株式会社喜多村制造的“KT-300M(商品名)”等。此外,除了上述以外,还能够使用用苯乙烯类、丙烯酸酯类、甲基丙烯酸酯类、丙烯腈类聚合物等改性的PTFE。具体而言,可以列举MITSUBISHI RAYON CO.,LTD.制造的“METABLEN A-3000(商品名)”等。高分子量PTFE的配合量通常为0.5~10体积%,优选为0.5~5体积%。如果高分子量PTFE的配合量不足0.5体积%,则不能充分发挥上述的作用,而配合超过10体积%,则不仅使耐磨损性降低,而且有可能导致成型性的降低。
使用亨舍尔混合机、高速混合机、球磨机、转鼓混合机等的混合机,混合上述的各成分的规定量,成型得到的混合物,即可制得本发明的固体润滑剂。成型方法,虽然并不特别限定,但是优选使用下述的方法:向挤出成型机供给上述混合物,在聚酰胺树脂可熔融的温度下熔融混炼该混合物,制作粒料,将该粒料供给至注射成型机,在作为结合材料的聚乙烯树脂的熔点以上的温度下进行成型。
本发明的滑动部件,在由金属材料或合成树脂材料形成的滑动部件基体的滑动面形成的孔或槽内埋入使用上述制造方法制得的固体润滑剂而得到。作为在该基体上形成的孔或槽内埋入固体润滑剂的方法,可以列举压入固定的方法、在固体润滑剂上涂布粘合剂后将其固定于孔或槽内的方法等。本发明的滑动部件,由于其在与配合部件的滑动中、在滑动面形成埋入该滑动面的固体润滑剂的膜,所以即使在反复的摩擦中也能够发挥低摩擦性、优良的耐磨损性,并且,埋入滑动面的固体润滑剂能够使机械强度提高。因此,在滑动部件的使用中,不会产生该固体润滑剂的缺损等的问题。
实施例
以下,列举实施例,更详细地说明本发明,本发明只要不超出其主旨,并不限定于以下的实施例。
实施例1、2
将作为聚乙烯树脂的低密度聚乙烯树脂(住友精化株式会社制造的“Fluothane(商品名)”)和/或高分子量聚乙烯树脂(三井化学株式会社制造的“LUBMER(商品名)”)的合计量5体积%、三聚氰胺氰脲酸酯(三菱化学株式会社制造的「MCA(商品名)」)40体积%、作为烃类蜡的石蜡20体积%和聚乙烯蜡20体积%、聚酰胺树脂(尼龙-12、Daicel-Evonik Ltd.制造的“VESTOSINT(商品名)”)10体积%、改性聚乙烯树脂(三井化学株式会社制造的“ADMER(商品名)”)5体积%投入亨舍尔混合机混合,将得到的混合物供给至挤出成型机,在聚酰胺树脂可熔融的温度下熔融混炼该混合物,制作粒料。接着,将该粒料供给至注射成型机,在聚乙烯树脂熔融的温度下进行成型,制得直径为6mm、长度为5mm的圆柱状固体润滑剂。
实施例3~9
在实施例1、2中,如表2~表3所示改变成分组成,除此之外,使用与实施例1、2相同的方法,制得直径为6mm、长度为5mm的圆柱状固体润滑剂。
比较例1
将作为聚乙烯树脂的直链低密度聚乙烯树脂(LLDPE)50体积%、三聚氰胺氰脲酸酯50体积%投入亨舍尔混合机混合,将得到的混合物供给至挤出成型机,制得粒料。接着,将该粒料供给至注射成型机,制得直径为6mm、长度为5mm的圆柱状固体润滑剂。
比较例2
将作为聚乙烯树脂的低密度聚乙烯树脂(LDPE)10体积%、作为烃类蜡的石蜡13体积%、作为金属皂的硬脂酸锂7体积%、铅40体积%、作为四氟乙烯树脂的低分子量四氟乙烯树脂30体积%投入亨舍尔混合机混合,将得到的混合物供给至挤出成型机,制得粒料。接着,将该粒料供给至注射成型机,制得直径为6mm、长度为5mm的圆柱状固体润滑剂。
比较例3
将作为聚乙烯树脂的低密度聚乙烯树脂(LDPE)20体积%、作为烃类蜡的石蜡12.5体积%和聚乙烯蜡12.5体积%、三聚氰胺氰脲酸酯30体积%、作为高级脂肪酸酯的褐煤蜡5体积%、作为金属皂的硬脂酸锂10体积%、作为磷酸盐的磷酸三锂5体积%、高分子量PTFE5体积%投入亨舍尔混合机混合,将得到的混合物供给至挤出成型机,在烃类蜡熔融的温度下熔融混炼该混合物,制得粒料。接着,将该粒料供给至注射成型机,在聚乙烯树脂的熔点以上的温度下进行成型,制得直径为6mm、长度为5mm的圆柱状固体润滑剂。
比较例4
在比较例3中,使用聚酰胺树脂(尼龙-12)20体积%代替聚乙烯树脂20体积%,除此之外,使用与比较例3相同的成分,制得混合物,向挤出成型机供给该混合物,在聚酰胺树脂熔融的温度下熔融混炼该混合物,制得粒料。接着,将该粒料供给至注射成型机,在聚酰胺树脂熔融的温度下进行成型,制得直径为6mm、长度为5mm的圆柱状固体润滑剂。
比较例5
将作为聚乙烯树脂的低密度聚乙烯树脂(LDPE)10体积%、作为烃类蜡的石蜡20体积%和聚乙烯蜡20体积%、三聚氰胺氰脲酸酯40体积%、聚酰胺树脂(尼龙-12)10体积%投入亨舍尔混合机混合,将得到的混合物供给至挤出成型机,在聚酰胺树脂熔融的温度下熔融混炼该混合物,制得粒料。接着,将该粒料供给至注射成型机,在聚乙烯树脂的熔点以上的温度下进行成型,制得直径为6mm、长度为5mm的圆柱状固体润滑剂。
将在上述实施例和比较例中得到的固体润滑剂埋入在由铜合金形成的平板状基体的滑动面上形成的孔内,制得滑动部件试验片,在如表1所示的试验条件下,通过推力试验,测定摩擦系数和磨耗量。此外,作为固体润滑剂的机械性质,测定压缩强度(N/mm2)。将推力试验的结果和压缩强度的测定结果表示于表2~表4。
表1
试验片材质 | 4种高力黄铜铸物 |
配合材料材质 | 不锈钢(SUS304) |
固体润滑剂占有的滑动面的面积比例 | 30% |
滑行速度 | 1m/min |
负荷 | 29.4MPa(300kgf/cm2) |
润滑 | 无润滑 |
试验时间 | 8小时 |
表2
表3
表4
如以上的试验结果所明示,本发明的固体润滑剂(实施例1~实施例9)的压缩强度,与比较例3的压缩强度(在本发明的发明人之前提案的专利文献2中记载的固体润滑剂)相比,大幅度地提高,并且,未见埋入滑动面的固体润滑剂在试验后缺损。与此对照,就比较例3和比较例5的固体润滑剂而言,已确认:埋入滑动面的固体润滑剂在试验后被若干掘出而缺损。根据滑动特性的试验结果,埋入本发明的固体润滑剂而构成的滑动部件,呈现优良的滑动特性,并呈现与埋入如比较例2所示作为现有技术的含有铅的固体润滑剂而构成的滑动部件同等或其以上的性能。另外,本发明的固体润滑剂,即使与比较例2相比,也呈现同等的性能。再者,就埋入比较例1和比较例4的固体润滑剂的滑动部件而言,因为试验中摩擦系数超过0.2,所以中途停止了试验。
Claims (11)
1.一种固体润滑剂,其特征在于,包括:
1~10体积%的聚乙烯树脂、20~60体积%的烃类蜡、10~60体积%的三聚氰胺氰脲酸酯、5~15体积%的聚酰胺树脂、2~10体积%的改性聚乙烯树脂。
2.如权利要求1所述的固体润滑剂,其特征在于:
烃类蜡是石蜡、聚乙烯蜡、烷基苯、微晶蜡或它们的两种以上的混合物。
3.如权利要求1或2中所述的固体润滑剂,其特征在于:
聚酰胺是聚十二内酰胺(尼龙-12)和/或聚十一内酰胺(尼龙-11)。
4.如权利要求1~3中任一项所述的固体润滑剂,其特征在于:
改性聚乙烯树脂是使接枝单体与聚乙烯树脂接枝聚合而得到的接枝改性聚乙烯树脂。
5.如权利要求4所述的固体润滑剂,其特征在于:
接枝单体是α,β-不饱和羧酸、α,β-不饱和羧酸酐、α,β-不饱和羧酸衍生物或它们的两种以上。
6.如权利要求1~5中任一项所述的固体润滑剂,其特征在于:
作为补加成分,还含有1~10体积%的高级脂肪酸、高级脂肪酸酯、高级脂肪酸酰胺或它们的两种以上。
7.如权利要求1~6中任一项所述的固体润滑剂,其特征在于:
作为补加成分,还含有3~20体积%的金属皂。
8.如权利要求1~7中任一项所述的固体润滑剂,其特征在于:
作为补加成分,还含有3~15体积%的磷酸盐。
9.如权利要求1~8中任一项所述的固体润滑剂,其特征在于:
作为补加成分,还含有0.5~10体积%的高分子量的四氟乙烯树脂。
10.如权利要求1~9中任一项所述的固体润滑剂,其特征在于:
埋入在滑动部件基体的滑动面上形成的孔或槽内。
11.一种滑动部件,其特征在于:
该滑动部件通过在滑动部件基体的滑动面上形成的孔或槽内埋入权利要求1~10中任一项所述的固体润滑剂而构成。
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CN106151278A (zh) * | 2015-03-02 | 2016-11-23 | 大同金属工业株式会社 | 水中滑动构件 |
CN110951519A (zh) * | 2019-12-06 | 2020-04-03 | 平湖市凯丰机械制造有限公司 | 水润滑固体润滑柱及其制作方法 |
CN115605544A (zh) * | 2020-04-21 | 2023-01-13 | 奥依列斯工业株式会社(Jp) | 聚酰胺树脂组合物和滑动元件 |
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JP5696983B2 (ja) | 2015-04-08 |
CA2662334A1 (en) | 2008-03-13 |
EP2060620A4 (en) | 2010-12-01 |
CA2662334C (en) | 2014-04-22 |
JPWO2008029510A1 (ja) | 2010-01-21 |
US20100048433A1 (en) | 2010-02-25 |
EP2060620A1 (en) | 2009-05-20 |
EP2060620B1 (en) | 2013-04-24 |
JP2013108096A (ja) | 2013-06-06 |
WO2008029510A1 (fr) | 2008-03-13 |
KR20090049059A (ko) | 2009-05-15 |
KR101412268B1 (ko) | 2014-06-25 |
JP5414275B2 (ja) | 2014-02-12 |
US8202825B2 (en) | 2012-06-19 |
CN101522874B (zh) | 2013-06-05 |
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