JP2010059396A - Solid lubricant and method of manufacturing the same - Google Patents
Solid lubricant and method of manufacturing the same Download PDFInfo
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- JP2010059396A JP2010059396A JP2009142954A JP2009142954A JP2010059396A JP 2010059396 A JP2010059396 A JP 2010059396A JP 2009142954 A JP2009142954 A JP 2009142954A JP 2009142954 A JP2009142954 A JP 2009142954A JP 2010059396 A JP2010059396 A JP 2010059396A
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- 239000007787 solid Substances 0.000 title claims abstract description 58
- 239000000314 lubricant Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000007770 graphite material Substances 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 37
- 239000010410 layer Substances 0.000 claims abstract description 35
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 33
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 33
- 239000011229 interlayer Substances 0.000 claims abstract description 30
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000010452 phosphate Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000010306 acid treatment Methods 0.000 claims description 10
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 31
- 239000010439 graphite Substances 0.000 abstract description 31
- 239000002253 acid Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 10
- 238000009830 intercalation Methods 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 230000002687 intercalation Effects 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002783 friction material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000005461 lubrication Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PBQAYLNBRDAQQX-UHFFFAOYSA-N 2-ethylhexyl(trimethoxy)silane Chemical compound CCCCC(CC)C[Si](OC)(OC)OC PBQAYLNBRDAQQX-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- DLRHRQTUCJTIIV-UHFFFAOYSA-N diethoxy(ethyl)alumane Chemical compound CC[O-].CC[O-].CC[Al+2] DLRHRQTUCJTIIV-UHFFFAOYSA-N 0.000 description 1
- VIOFGSVPZIUESI-UHFFFAOYSA-N diethoxy(propyl)alumane Chemical compound CCC[Al](OCC)OCC VIOFGSVPZIUESI-UHFFFAOYSA-N 0.000 description 1
- KZMMGHBBGSVIKO-UHFFFAOYSA-N diethoxyaluminum Chemical compound CCO[Al]OCC KZMMGHBBGSVIKO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- VICYBMUVWHJEFT-UHFFFAOYSA-N dodecyltrimethylammonium ion Chemical group CCCCCCCCCCCC[N+](C)(C)C VICYBMUVWHJEFT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- UABOHUHCGKGGOJ-UHFFFAOYSA-N ethyl(dimethoxy)alumane Chemical compound [O-]C.[O-]C.CC[Al+2] UABOHUHCGKGGOJ-UHFFFAOYSA-N 0.000 description 1
- LNSLFANJWYSGQS-UHFFFAOYSA-N hex-2-enyl(trimethoxy)silane Chemical compound CCCC=CC[Si](OC)(OC)OC LNSLFANJWYSGQS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DKUIXLPCCDROFD-UHFFFAOYSA-N methanolate;methylaluminum(2+) Chemical compound [O-]C.[O-]C.[Al+2]C DKUIXLPCCDROFD-UHFFFAOYSA-N 0.000 description 1
- FTWKTOVWPKRLHM-UHFFFAOYSA-N methoxyaluminum Chemical compound CO[Al] FTWKTOVWPKRLHM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JMRWHIBGEUIERH-UHFFFAOYSA-N methylaluminum(2+);propan-1-olate Chemical compound [Al+2]C.CCC[O-].CCC[O-] JMRWHIBGEUIERH-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- QDMRIYQNEDNXRO-UHFFFAOYSA-N trimethoxy(3-naphthalen-2-ylpropyl)silane Chemical compound C1=CC=CC2=CC(CCC[Si](OC)(OC)OC)=CC=C21 QDMRIYQNEDNXRO-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- DAOVYDBYKGXFOB-UHFFFAOYSA-N tris(2-methylpropoxy)alumane Chemical compound [Al+3].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] DAOVYDBYKGXFOB-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
Description
本発明は、固体潤滑材およびその製造方法に関する。
さらに詳しくは、本発明は、自動車、鉄道車両、産業機械等のブレーキ用摩擦材や、クラッチフェーシングの摩擦材に好適に使用し得る固体潤滑材およびその製造方法に関するものである。
The present invention relates to a solid lubricant and a manufacturing method thereof.
More specifically, the present invention relates to a solid lubricant that can be suitably used as a friction material for brakes of automobiles, railway vehicles, industrial machines, etc., and a friction material for clutch facing, and a method for manufacturing the same.
近年、ブレーキ用摩擦材等の分野においては、固体潤滑材として、グラファイト、二硫化モリブデン、ゼオライト等の層状無機物質や、ポリ四フッ化エチレン（ＰＴＦＥ）等の有機物質が用いられるようになってきている（例えば、特許文献１参照）。 In recent years, in the field of friction materials for brakes and the like, layered inorganic substances such as graphite, molybdenum disulfide, and zeolite, and organic substances such as polytetrafluoroethylene (PTFE) have come to be used as solid lubricants. (For example, refer to Patent Document 1).
しかしながら、上記固体潤滑材は、大気中、５００℃以上の高温域において、酸化、分解等して潤滑特性を維持できなくなってしまい、摩擦、異音等を増大させてしまうことから、ブレーキ用摩擦材等に用いるためには、必ずしも満足し得るものではなかった。 However, the above-mentioned solid lubricant cannot be maintained in lubrication characteristics due to oxidation, decomposition, etc. in the high temperature range of 500 ° C. or higher in the atmosphere, and increases friction, noise, etc. It was not always satisfactory for use as a material.
本発明は、このような事情のもとで、大気中、高温域においても酸化、分解等を抑制することができ、潤滑特性を維持することができ、さらには相手材に対する研削を抑制した固体潤滑材およびその製造方法を提供することを目的とするものである。 Under such circumstances, the present invention can suppress oxidation, decomposition, etc. even in the atmosphere and in a high temperature range, maintain lubrication characteristics, and further, solid that suppresses grinding of the counterpart material. It is an object of the present invention to provide a lubricant and a method for producing the same.
本発明者等が鋭意研究を重ねた結果、天然黒鉛よりも層間距離が拡大された黒鉛材料の少なくとも一部の表面に金属酸化物層、特にリン酸塩被覆層を有する金属酸化物層が被覆されてなる固体潤滑材により、上記目的を達成し得ることを見出し、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies by the present inventors, a metal oxide layer, particularly a metal oxide layer having a phosphate coating layer, is coated on at least a part of the surface of a graphite material whose interlayer distance is larger than that of natural graphite. It has been found that the above object can be achieved by the solid lubricant thus formed, and the present invention has been completed based on this finding.
すなわち、本発明は、
（１） 天然黒鉛よりも層間距離が拡大された黒鉛材料の少なくとも一部の表面に金属酸化物層が被覆されてなることを特徴とする固体潤滑材、
（２） 前記黒鉛材料の表面に中間層を介することなく、金属酸化物層が被覆されてなる上記（１）に記載の固体潤滑材、
（３） 前記黒鉛材料が有機官能基を導入したものである上記（１）または（２）に記載の固体潤滑材、
（４） 前記金属酸化物層が酸化ケイ素、酸化チタン、酸化アルミニウム、酸化ジルコニウムから選ばれる少なくとも一種を含んでなる上記（１）〜（３）のいずれか１項に記載の固体潤滑材、
（５） 前記黒鉛材料の表面に中間層を介することなく、金属酸化物層が被覆されてなり、かつ該金属酸化物層表面にさらにリン酸塩が被覆されてなる上記（１）、（３）または（４）に記載の固体潤滑材、
（６） 前記リン酸塩が第一リン酸アルミニウムである上記（５）に記載の固体潤滑材、
（７） 天然黒鉛を酸処理して層間距離が拡大された黒鉛材料を得た後に、該黒鉛材料と金属アルコキシドとを接触させ、次いで加熱処理することにより、黒鉛材料の少なくとも一部の表面に金属酸化物層を被覆することを特徴とする上記（１）〜（４）のいずれか１項に記載の固体潤滑材を製造する方法、
（８） 天然黒鉛を酸処理して層間距離が拡大された黒鉛材料を得た後に、該黒鉛材料と金属アルコキシドとを接触させ、次いで加熱処理して得られたものに、リン酸塩を接触させることにより、黒鉛材料の少なくとも一部の表面に、リン酸塩が被覆されてなる金属酸化物層を被覆することを特徴とする上記（５）または（６）に記載の固体潤滑材を製造する方法、及び
（９） 前記金属アルコキシドと接触させる前に、前記黒鉛材料の表面を、有機官能基導入処理する上記（７）または（８）に記載の方法
を提供するものである。
That is, the present invention
(1) A solid lubricant characterized in that a metal oxide layer is coated on at least a part of the surface of a graphite material having an interlayer distance larger than that of natural graphite,
(2) The solid lubricant according to (1) above, wherein the surface of the graphite material is coated with a metal oxide layer without an intermediate layer,
(3) The solid lubricant according to (1) or (2), wherein the graphite material has an organic functional group introduced therein,
(4) The solid lubricant according to any one of (1) to (3), wherein the metal oxide layer contains at least one selected from silicon oxide, titanium oxide, aluminum oxide, and zirconium oxide.
(5) The above (1), (3), wherein the surface of the graphite material is coated with a metal oxide layer without an intermediate layer, and the surface of the metal oxide layer is further coated with a phosphate. ) Or (4) a solid lubricant,
(6) The solid lubricant according to (5), wherein the phosphate is primary aluminum phosphate,
(7) After obtaining a graphite material having an increased interlayer distance by acid treatment of natural graphite, the graphite material and the metal alkoxide are brought into contact with each other, and then heat-treated, so that at least a part of the surface of the graphite material is applied. A method for producing a solid lubricant according to any one of the above (1) to (4), wherein the metal oxide layer is coated,
(8) After obtaining a graphite material having an increased interlayer distance by acid treatment of natural graphite, the graphite material and a metal alkoxide are brought into contact with each other, and then a heat treatment is performed to contact with phosphate. To produce a solid lubricant as described in (5) or (6) above, wherein at least a part of the surface of the graphite material is coated with a metal oxide layer coated with phosphate. And (9) The method according to (7) or (8) above, wherein the surface of the graphite material is subjected to an organic functional group introduction treatment before contacting with the metal alkoxide.
本発明によれば、大気中、高温域においても酸化、分解等を抑制することができ、潤滑特性を維持することができ、さらには相手材に対する研削を抑制した固体潤滑材およびその製造方法を提供することができる。 According to the present invention, a solid lubricant that can suppress oxidation, decomposition, etc. even in the atmosphere and in a high temperature range, maintain lubrication characteristics, and further suppress grinding on a counterpart material, and a method for manufacturing the same. Can be provided.
本発明の固体潤滑材は、天然黒鉛よりも層間距離が拡大された黒鉛材料の少なくとも一部の表面に金属酸化物層が被覆されてなることを特徴とするものである。 The solid lubricant of the present invention is characterized in that a metal oxide layer is coated on at least a part of the surface of a graphite material whose interlayer distance is larger than that of natural graphite.
本発明の固体潤滑材において、黒鉛材料としては、天然黒鉛よりも層間距離が拡大された層状構造を有するものであれば特に限定されないが、入手の容易性や価格面を考慮した場合、天然黒鉛である鱗状黒鉛や鱗片状黒鉛を後述する方法等によって処理したものであることが好ましい。 In the solid lubricant of the present invention, the graphite material is not particularly limited as long as it has a layered structure in which the interlayer distance is larger than that of natural graphite. However, in view of availability and price, natural graphite is used. It is preferable that the scaly graphite or scaly graphite is processed by the method described later.
また、本明細書において、「天然黒鉛よりも層間距離が拡大された」とは、天然黒鉛の層間距離である０．３３５４ｎｍよりも層間距離が拡大されていることを意味し、拡大された層間距離としては、０．５〜３ｎｍが好ましく、２〜３ｎｍがより好ましい。 Further, in the present specification, “the interlayer distance is expanded more than that of natural graphite” means that the interlayer distance is expanded more than 0.3354 nm, which is the interlayer distance of natural graphite. The distance is preferably 0.5 to 3 nm, and more preferably 2 to 3 nm.
このように層間距離が天然黒鉛よりも拡大された黒鉛材料を用いることにより、得られる固体潤滑材の潤滑性を向上させることができる。 Thus, the lubricity of the obtained solid lubricant can be improved by using a graphite material whose interlayer distance is larger than that of natural graphite.
本発明の固体潤滑材において、金属酸化物層としては、酸化ケイ素、酸化チタン、酸化アルミニウム、酸化ジルコニウムから選ばれる少なくとも一種を含んでなるものであることが好ましく、上記金属酸化物から選ばれる一種のみを含んでなるものであることがより好ましい。 In the solid lubricant of the present invention, the metal oxide layer preferably contains at least one selected from silicon oxide, titanium oxide, aluminum oxide, and zirconium oxide, and is selected from the above metal oxides It is more preferable that it contains only.
本発明の固体潤滑材は、金属酸化物層が、黒鉛材料の少なくとも一部の表面に被覆されてなるものであるが、黒鉛材料最外部の表面全体に被覆されてなるものであることがより好ましい。 In the solid lubricant of the present invention, the metal oxide layer is coated on at least a part of the surface of the graphite material, but is more preferably coated on the entire outermost surface of the graphite material. preferable.
金属酸化物層の厚みは、５０〜３００ｎｍであることが好ましく、５０〜１００ｎｍであることがより好ましい。 The thickness of the metal oxide layer is preferably 50 to 300 nm, and more preferably 50 to 100 nm.
本発明の固体潤滑材においては、前記黒鉛材料の表面に中間層を介することなく金属酸化物層が被覆されていることが好ましく、これにより、固体潤滑材の製造工程を簡略化し、製造コストを低減することが可能になる。 In the solid lubricant of the present invention, the surface of the graphite material is preferably coated with a metal oxide layer without an intermediate layer, thereby simplifying the production process of the solid lubricant and reducing the production cost. It becomes possible to reduce.
また、下記の理由により、前記金属酸化物層には、その表面にさらにリン酸塩を被覆することが好ましい。 For the following reasons, it is preferable that the surface of the metal oxide layer is further coated with phosphate.
層間距離が拡大された黒鉛材料の少なくとも一部の表面に金属酸化物を被覆し、層間拡大により高温域での潤滑特性を維持しているが、前記金属酸化物層は酸化ケイ素、酸化チタン、酸化アルミニウム、酸化ジルコニウムから選ばれる少なくとも一種を含んでおり、高温域における摩擦時に相手材（ブレーキロータ）を研削する効果が大きくなる。したがって、金属酸化物層の表面にさらに研削作用が小さく耐熱性を劣化させないリン酸塩を被覆することにより、相手材の研削を抑制して長期安定した制動が維持される。 The surface of at least a part of the graphite material whose interlayer distance is expanded is coated with a metal oxide, and the lubrication characteristics in the high temperature range are maintained by the interlayer expansion, but the metal oxide layer includes silicon oxide, titanium oxide, It contains at least one selected from aluminum oxide and zirconium oxide, and the effect of grinding the mating material (brake rotor) during friction in a high temperature range is increased. Therefore, by covering the surface of the metal oxide layer with a phosphate that has a smaller grinding action and does not deteriorate the heat resistance, grinding of the counterpart material is suppressed and long-term stable braking is maintained.
前記リン酸塩としては特に制限はないが、効果の観点から、第一リン酸アルミニウムが好ましい。 Although there is no restriction | limiting in particular as said phosphate, From a viewpoint of an effect, primary aluminum phosphate is preferable.
本発明の固体潤滑材においては、前記黒鉛材料が有機官能基を導入してなるものであってもよい。 In the solid lubricant of the present invention, the graphite material may be an organic functional group introduced.
有機官能基としては、有機化アンモニウム基、有機化アミノ基、有機化ジアミノ基、有機化アミノカルボキシル基等を挙げることができる。有機化アンモニウム基としては、アルキルアンモニウム基を挙げることができ、具体的には、ドデシルトリメチルアンモニウム基等を挙げることができる。有機化アミノ基としては、アルキルアミノ基を挙げることができ、具体的には、ドデシルアミノ基、オクタデシルアミノ基等を挙げることができる。有機化ジアミノ基としては、アルキルジアミノ基を挙げることができ、具体的には、１，１２−ドデカンジアミノ基等を挙げることができる。また、有機化アミノカルボキシル基としては、アルキルアミノカルボキシル基を挙げることができ、具体的には、１２−アミノドデカン酸等を挙げることができる。 Examples of the organic functional group include an organized ammonium group, an organized amino group, an organized diamino group, and an organized amino carboxyl group. Examples of the organized ammonium group include an alkylammonium group, and specific examples include a dodecyltrimethylammonium group. Examples of the organic amino group include an alkylamino group, and specific examples include a dodecylamino group and an octadecylamino group. Examples of the organic diamino group include an alkyl diamino group, and specifically include a 1,12-dodecanediamino group. Examples of the organic aminocarboxyl group include alkylaminocarboxyl groups, and specific examples include 12-aminododecanoic acid.
本発明の固体潤滑材を製造する好適な方法としては、以下に説明する本発明の固体潤滑材の製造方法を挙げることができる。 As a suitable method for producing the solid lubricant of the present invention, the method for producing the solid lubricant of the present invention described below can be exemplified.
本発明の固体潤滑材の製造方法は、天然黒鉛を酸処理して層間距離が拡大された黒鉛材料を得た後に、該黒鉛材料と金属アルコキシドとを接触させ、次いで加熱処理することにより、黒鉛材料の少なくとも一部の表面に金属酸化物層を被覆することを特徴とするものである。 The method for producing a solid lubricant according to the present invention provides a graphite material obtained by acid-treating natural graphite to obtain a graphite material having an increased interlayer distance, contacting the graphite material with a metal alkoxide, and then heat-treating the graphite material. A metal oxide layer is coated on at least a part of the surface of the material.
本発明の方法において、原料として用いられる天然黒鉛としては、特に限定されず、鱗片状黒鉛、鱗状黒鉛等を用いることができる。 In the method of the present invention, the natural graphite used as a raw material is not particularly limited, and scaly graphite, scaly graphite or the like can be used.
本発明の方法において、酸処理に用いられる酸としては、硫酸、硝酸等を挙げることができ、また、酸処理においては酸化剤を併用することが好ましく、酸化剤としては、濃硝酸等を挙げることができる。 In the method of the present invention, examples of the acid used for the acid treatment include sulfuric acid and nitric acid. In the acid treatment, an oxidizing agent is preferably used in combination, and the oxidizing agent includes concentrated nitric acid. be able to.
上記酸の使用量は、天然黒鉛の全表面と接触し得る量であることが好ましいが、通常、酸：黒鉛（体積比）で、１００：１〜１００：２０であることが好ましい。 The amount of the acid used is preferably an amount that can come into contact with the entire surface of natural graphite, but is usually acid: graphite (volume ratio), preferably 100: 1 to 100: 20.
本発明の方法においては、上記酸処理によって、黒鉛材料の層間距離を天然黒鉛の層間距離よりも拡大し、得られる固体潤滑材の潤滑性を向上させることができるとともに、黒鉛の主表面や端部表面に官能基を導入して、後述する金属アルコキシドとの反応性を向上させることができる。 In the method of the present invention, by the acid treatment, the interlayer distance of the graphite material can be made larger than the interlayer distance of natural graphite, the lubricity of the resulting solid lubricant can be improved, and the main surface and edges of the graphite can be improved. By introducing a functional group to the surface of the part, the reactivity with the metal alkoxide described later can be improved.
酸処理によって黒鉛表面に導入される官能基としては、ＯＨ基、ＣＯＯＨ基、ＣＯ基等を挙げることができる。 Examples of the functional group introduced onto the graphite surface by the acid treatment include OH group, COOH group, CO group and the like.
本発明の方法においては、上記酸処理後に、さらに有機官能基導入処理を行うことが好ましい。 In the method of the present invention, it is preferable to further perform an organic functional group introduction treatment after the acid treatment.
導入される有機官能基としては、有機化アンモニウムやその塩に由来する有機化アンモニウム基、有機化アミンやその塩に由来する有機化アミノ基、有機化ジアミンに由来する有機化ジアミノ基、有機化アミノカルボン酸に由来する有機化アミノカルボキシル基等を挙げることができる。上記有機官能基の具体例については、上述したとおりである。 Organic functional groups to be introduced include organic ammonium groups derived from organic ammonium and salts thereof, organic amino groups derived from organic amines and salts thereof, organic diamino groups derived from organic diamines, organic compounds An organic aminocarboxyl group derived from aminocarboxylic acid can be mentioned. Specific examples of the organic functional group are as described above.
上述したように、本発明の方法においては、酸処理によって黒鉛表面に官能基を導入することができるが、さらに有機官能基導入処理を行うことにより、有機官能基を導入しつつ、酸処理後における黒鉛材料の拡大された層間距離を維持することができる。 As described above, in the method of the present invention, a functional group can be introduced to the graphite surface by acid treatment, but further, after introducing an organic functional group by performing an organic functional group introduction treatment, The expanded interlayer distance of the graphite material at can be maintained.
本発明の方法においては、次いで、黒鉛材料が金属アルコキシドと接触させられる。
金属アルコキシドとしては、特に限定されないが、一般式（Ｉ）
ＲｎＭＸｍ−ｎ ・・・（Ｉ）
（式中、Ｒは非加水分解性基、Ｘは加水分解性基または水酸基であり、Ｍはケイ素、チタン、ジルコニウムおよびアルミニウムの中から選ばれる金属原子を示し、ｍは金属原子Ｍの価数で、３または４であり、ｎは、ｍが４の場合は０〜３の整数、ｍが３の場合は０〜２の整数であり、
Ｒが複数ある場合、各Ｒはたがいに同一であっても異なっていてもよく、Ｘが複数ある場合、各Ｘはたがいに同一であっても異なっていてもよい。）で表される金属アルコキシドであることが好ましい。
In the method of the present invention, the graphite material is then contacted with a metal alkoxide.
Although it does not specifically limit as a metal alkoxide, General formula (I)
R n MX m−n (I)
Wherein R is a non-hydrolyzable group, X is a hydrolyzable group or a hydroxyl group, M is a metal atom selected from silicon, titanium, zirconium and aluminum, and m is the valence of the metal atom M And n is an integer from 0 to 3 when m is 4, and an integer from 0 to 2 when m is 3.
When there are a plurality of Rs, each R may be the same or different, and when there are a plurality of Xs, each X may be the same or different. It is preferable that it is a metal alkoxide represented by this.
一般式（Ｉ）で表される化合物において、ｍが４の場合、ｎは０〜３の整数であり、１〜３の整数であることが好ましく、１〜２の整数であることがより好ましい。また、ｍが３の場合、ｎは０〜２の整数であり、１〜２の整数であることが好ましい。 In the compound represented by the general formula (I), when m is 4, n is an integer of 0 to 3, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. . Moreover, when m is 3, n is an integer of 0-2, and it is preferable that it is an integer of 1-2.
一般式（Ｉ）で表される金属アルコキシドにおいて、Ｒは炭化水素基である。炭化水素基としては、直鎖または分岐鎖を有する飽和または不飽和の脂肪族炭化水素基、芳香族炭化水素基、脂環式炭化水素基を挙げることができ、これら炭化水素基は一価のものでも多価のものでもよい。 In the metal alkoxide represented by the general formula (I), R is a hydrocarbon group. Examples of the hydrocarbon group include a saturated or unsaturated aliphatic hydrocarbon group having a straight chain or a branched chain, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group. These hydrocarbon groups are monovalent. Or multivalent.
Ｒで表される炭化水素基の炭素数は、脂肪族炭化水素基である場合は、１〜２５個、特に１〜３個が好ましく、芳香族炭化水素基である場合は、６〜２５個、特に６〜１０個が好ましく、脂環式炭化水素である場合は、３〜２５個、特に３〜６個が好ましい。 The number of carbon atoms of the hydrocarbon group represented by R is preferably 1 to 25, particularly 1 to 3 in the case of an aliphatic hydrocarbon group, and 6 to 25 in the case of an aromatic hydrocarbon group. Particularly, 6 to 10 are preferable, and in the case of alicyclic hydrocarbon, 3 to 25, particularly 3 to 6 are preferable.
また、Ｒで表される炭化水素基は、官能基を含有していてもよく、官能基としては、ビニル基、エステル基、エーテル基、エポキシ基、アミノ基、カルボキシル基、カルボニル基、アミド基、メルカプト基、スルホニル基、スルフェニル基、ニトロ基、ニトロソ基、ニトリル基、ハロゲン原子、水酸基等を挙げることができる。 Further, the hydrocarbon group represented by R may contain a functional group, and examples of the functional group include a vinyl group, an ester group, an ether group, an epoxy group, an amino group, a carboxyl group, a carbonyl group, and an amide group. , Mercapto group, sulfonyl group, sulfenyl group, nitro group, nitroso group, nitrile group, halogen atom, hydroxyl group and the like.
一般式（Ｉ）で表される金属アルコキシドにおいて、Ｒが複数ある場合、Ｒは同一であっても異なっていてもよい。 In the metal alkoxide represented by the general formula (I), when there are a plurality of Rs, the Rs may be the same or different.
一般式（Ｉ）で表される金属アルコキシドにおいて、Ｘは加水分解性基または水酸基であり、加水分解性基としては、アルコキシ基、アルケニルオキシ基、ケトオキシム基、アシルオキシ基、アミノ基、アミノキシ基、アミド基、ハロゲン原子を挙げることができる。 In the metal alkoxide represented by the general formula (I), X is a hydrolyzable group or a hydroxyl group, and examples of the hydrolyzable group include an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, Examples include amide groups and halogen atoms.
一般式（Ｉ）で表される金属アルコキシドにおいて、Ｘが複数ある場合、Ｘは同一であっても異なっていてもよい。 In the metal alkoxide represented by the general formula (I), when there are a plurality of Xs, Xs may be the same or different.
上記一般式（Ｉ）で表される金属アルコキシドにおいて、Ｍが４価のケイ素であって、ｍが４で、ｎが０〜３の整数である場合の金属アルコキシドの具体例としては、テトラエトキシシラン、テトライソプロポキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、２−エチルヘキシルトリメトキシシラン、２−ヘキセニルトリメトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、３−β−ナフチルプロピルトリメトキシシラン、ｐ−ビニルベンジルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリクロロシラン、ビニルトリアセトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−アニリノプロピルトリメトキシシラン等を挙げることができる。 In the metal alkoxide represented by the above general formula (I), specific examples of the metal alkoxide in the case where M is tetravalent silicon, m is 4, and n is an integer of 0 to 3 include tetraethoxy Silane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-hexenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-β-naphthylpropyltrimethoxysilane , P-vinylbenzyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-anilinopropyl Trimethoxy Mention may be made of the run, and the like.
上記一般式（Ｉ）で表される化合物において、Ｍが４価のチタンまたはジルコニウムであって、ｍが４で、ｎが０〜３の整数である場合の金属アルコキシドの例としては、上で例示したシラン化合物におけるシランを、チタンまたはジルコニウムに置き換えた化合物を挙げることができる。 Examples of the metal alkoxide in the case where M is tetravalent titanium or zirconium, m is 4, and n is an integer of 0 to 3 in the compound represented by the above general formula (I) The compound which replaced the silane in the illustrated silane compound with titanium or zirconium can be mentioned.
また、前記一般式（Ｉ）で表される金属アルコキシドにおいて、Ｍが３価のアルミニウムであって、ｍが３で、ｎが０〜２の整数である場合の金属アルコキシドの例としては、トリメトキシアルミニウム、トリエトキシアルミニウム、トリ−ｎ−プロポキシアルミニウム、トリイソプロポキシアルミニウム、トリ−ｎ−ブトキシアルミニウム、トリイソブトキシアルミニウム、トリ−ｓｅｃ−ブトキシアルミニウム、トリ−ｔｅｒｔ−ブトキシアルミニウム、メチルジメトキシアルミニウム、メチルジエトキシアルミニウム、メチルジプロポキシアルミニウム、エチルジメトキシアルミニウム、エチルジエトキシアルミニウム、プロピルジエトキシアルミニウムなどを挙げることができる。 Examples of the metal alkoxide represented by the general formula (I) in the case where M is trivalent aluminum, m is 3, and n is an integer of 0 to 2 include tri Methoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, triisopropoxy aluminum, tri-n-butoxy aluminum, triisobutoxy aluminum, tri-sec-butoxy aluminum, tri-tert-butoxy aluminum, methyl dimethoxy aluminum, methyl Examples include diethoxyaluminum, methyldipropoxyaluminum, ethyldimethoxyaluminum, ethyldiethoxyaluminum, and propyldiethoxyaluminum.
上記金属アルコキシドは、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。 The said metal alkoxide may be used individually by 1 type, and may be used in combination of 2 or more type.
黒鉛材料と前記金属アルコキシドとを接触させる方法としては、例えば、硝酸水溶液等により膨潤、分散させた黒鉛材料と、エタノール等で希釈した金属アルコキシドとを、室温または加熱条件下で混合、攪拌する方法を挙げることができる。 As a method of bringing the graphite material and the metal alkoxide into contact, for example, a method of mixing and stirring a graphite material swollen and dispersed in an aqueous nitric acid solution and a metal alkoxide diluted with ethanol or the like at room temperature or under heating conditions Can be mentioned.
黒鉛材料と金属アルコキシドは、質量比で、黒鉛材料／金属アルコキシドが、１／０．５〜１／４となるように使用することが好ましく、１／０．５〜１／２となるように使用することがより好ましい。 It is preferable to use the graphite material and the metal alkoxide so that the graphite material / metal alkoxide is 1 / 0.5 to 1/4, and 1 / 0.5 to 1/2 by mass ratio. More preferably it is used.
また、上述したような方法により、黒鉛材料と金属アルコキシドとを混合、攪拌させる場合には、金属アルコキシドの疎水基の耐熱性を考慮して、混合、攪拌時の温度を決定する必要があることから、黒鉛材料と金属アルコキシドの反応温度は、室温〜１００℃程度が好ましい。また、反応時間は２〜４８時間が好ましい。 In addition, when the graphite material and the metal alkoxide are mixed and stirred by the method described above, it is necessary to determine the temperature during mixing and stirring in consideration of the heat resistance of the hydrophobic group of the metal alkoxide. Therefore, the reaction temperature between the graphite material and the metal alkoxide is preferably about room temperature to 100 ° C. The reaction time is preferably 2 to 48 hours.
このように、黒鉛材料と金属アルコキシドとを接触させることにより、黒鉛材料表面に導入された官能基と金属アルコキシドの加水分解性基または水酸基とが反応ないし相互作用して、黒鉛材料表面に金属アルコキシドが固定されると考えられる。 As described above, when the graphite material and the metal alkoxide are brought into contact with each other, the functional group introduced on the surface of the graphite material reacts with or interacts with the hydrolyzable group or hydroxyl group of the metal alkoxide, thereby causing the metal alkoxide on the surface of the graphite material. Is considered fixed.
本発明の方法においては、次いで、黒鉛材料と金属アルコキシドの接触処理物が加熱処理されて、黒鉛材料の少なくとも一部の表面に金属酸化物層が被覆される。加熱温度は４００℃〜１０００℃が好ましい。加熱時間や加熱雰囲気は、金属アルコキシドの種類に応じて適宜選定される。 In the method of the present invention, the contact-treated product of the graphite material and the metal alkoxide is then heat-treated so that at least a part of the surface of the graphite material is coated with the metal oxide layer. The heating temperature is preferably 400 ° C to 1000 ° C. The heating time and the heating atmosphere are appropriately selected according to the type of metal alkoxide.
本発明の固体潤滑材においては、前述したように、相手材に対する研削を抑制して、長期安定した制動を維持するために、前記金属酸化物の表面に、さらに研削作用が小さく耐熱性を劣化させないリン酸塩を被覆することが好ましい。したがって、固体潤滑材の好適な製造方法として、天然黒鉛を酸処理して層間距離が拡大された黒鉛材料を得た後に、該黒鉛材料と金属アルコキシドとを接触させ、次いで加熱処理して得られたものに、リン酸塩を接触させることにより、黒鉛材料の少なくとも一部の表面に、リン酸塩が被覆されてなる金属酸化物層を被覆する方法を用いることができる。 In the solid lubricant of the present invention, as described above, in order to suppress grinding against the counterpart material and maintain stable braking over a long period of time, the surface of the metal oxide has a smaller grinding action and deteriorates heat resistance. It is preferable to coat a phosphate that does not occur. Therefore, as a suitable method for producing a solid lubricant, it is obtained by acid-treating natural graphite to obtain a graphite material having an increased interlayer distance, contacting the graphite material with a metal alkoxide, and then heat-treating. A method of coating a metal oxide layer formed by coating a phosphate on at least a part of the surface of the graphite material by bringing a phosphate into contact therewith can be used.
この製造方法において、層間距離が拡大された黒鉛材料と金属アルコキシドとを接触させ、次いで加熱処理して得られた反応物（金属酸化物を層間挿入した黒鉛層間化合物）にリン酸塩を接触させる方法としては、前記黒鉛層間化合物と、濃度０．５〜１０質量％程度、好ましく０．５〜５質量％のリン酸塩水溶液とを、質量比１：１〜５、好ましくは１：２程度の割合で、かつ２０〜８０℃程度の温度にて接触させる方法を用いることができる。前記リン酸塩としては、第一リン酸アルミニウムが好ましい。 In this manufacturing method, a graphite material having an expanded interlayer distance is brought into contact with a metal alkoxide, and then a phosphate is brought into contact with a reaction product (a graphite intercalation compound having an intercalated metal oxide) obtained by heat treatment. As the method, the graphite intercalation compound and a phosphate aqueous solution having a concentration of about 0.5 to 10% by mass, preferably 0.5 to 5% by mass, are in a mass ratio of 1: 1 to 5, preferably about 1: 2. And a method of contacting at a temperature of about 20 to 80 ° C. can be used. As the phosphate, primary aluminum phosphate is preferable.
前記加熱処理して得られた反応物、あるいは該反応物にリン酸塩を接触させたものを適宜粉砕、分級処理することにより、所望形状および所望サイズを有する固体潤滑材を得ることができる。 A solid lubricant having a desired shape and a desired size can be obtained by appropriately pulverizing and classifying a reaction product obtained by the heat treatment or a product obtained by bringing a phosphate into contact with the reaction product.
次に、本発明を実施例により、さらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
実施例１
ビーカー中に、黒鉛原料である天然鱗片状黒鉛（日本黒鉛社製、平均粒径５０μｍ、層間距離０．３３５４ｎｍ）５０ｇと、酸溶液である濃硫酸８００ｇおよび酸化剤である濃硝酸５０ｇとを加え、常温で２４時間攪拌することにより、黒鉛材料含有スラリーを作製した。
Example 1
In a beaker, 50 g of natural scaly graphite (Nippon Graphite Co., Ltd., average particle size 50 μm, interlayer distance 0.3354 nm) as a graphite raw material, 800 g of concentrated sulfuric acid as an acid solution and 50 g of concentrated nitric acid as an oxidizing agent are added. The slurry containing graphite material was prepared by stirring for 24 hours at room temperature.
また、金属アルコキシドであるテトラエトキシシラン（ＴＥＯＳ）、酢酸および水を、エタノール中に１：４：３のモル比になるように混合した後、７０℃で３時間加温し、濃縮して、１モル／リットルのテトラエトキシシラン含有液を得た。 In addition, tetraethoxysilane (TEOS), acetic acid and water, which are metal alkoxides, were mixed in ethanol at a molar ratio of 1: 4: 3, then heated at 70 ° C. for 3 hours, concentrated, A liquid containing 1 mol / liter of tetraethoxysilane was obtained.
黒鉛材料とテトラエトキシシラン含有液の質量比が７：３となるように、上記黒鉛材料含有スラリーとテトラエトキシシラン含有液とを混合し、室温で２４時間攪拌することにより、黒鉛材料とテトラエトキシシランとの接触物含有液を得た。得られた含有液を大気中１１０℃で２４時間乾燥した後解砕し、さらに窒素中８００℃で３時間熱処理して得られた固形物を乳鉢ですり潰すことにより、目的とする固体潤滑材の粉末を得た。 The graphite material-containing slurry and the tetraethoxysilane-containing liquid are mixed so that the mass ratio of the graphite material and the tetraethoxysilane-containing liquid is 7: 3, and stirred at room temperature for 24 hours. A liquid containing a contact product with silane was obtained. The obtained liquid was dried in the atmosphere at 110 ° C. for 24 hours, then crushed, and further solidified by heat treatment in nitrogen at 800 ° C. for 3 hours to crush it in a mortar to obtain the intended solid lubricant Of powder was obtained.
得られた固体潤滑材の粉末をＸ線回折装置（島津製作所社製ＸＲＤ−６０００）で測定したところ、黒鉛の層間が２ｎｍに拡大されていることを確認することができた。また、得られた固体潤滑材の粉末を電子顕微鏡（日立（株）社製ＨＤ−２０００）で測定したところ、表面全体に酸化ケイ素が被覆されていることを確認することができた。 When the obtained solid lubricant powder was measured with an X-ray diffractometer (XRD-6000, manufactured by Shimadzu Corporation), it was confirmed that the graphite interlayer was enlarged to 2 nm. Further, when the obtained solid lubricant powder was measured with an electron microscope (HD-2000 manufactured by Hitachi, Ltd.), it was confirmed that the entire surface was covered with silicon oxide.
実施例２
テトラエトキシシラン含有液に代えて、金属アルコキシドであるテトライソプロポキシチタン、酢酸および水を、エタノール中に１：４：３のモル比になるように混合した後、７０℃で３時間加温し、濃縮して得た、１モル／リットルのテトライソプロポキシチタン（ＴＩＰＯＴ）含有液を用いた以外は、実施例１と同様にして、目的とする固体潤滑材の粉末を得た。
Example 2
Instead of the tetraethoxysilane-containing liquid, a metal alkoxide, tetraisopropoxytitanium, acetic acid, and water were mixed in ethanol at a molar ratio of 1: 4: 3, and then heated at 70 ° C. for 3 hours. The target solid lubricant powder was obtained in the same manner as in Example 1 except that a 1 mol / liter tetraisopropoxy titanium (TIPOT) -containing liquid obtained by concentration was used.
得られた固体潤滑材の粉末をＸ線回折装置（島津製作所社製ＸＲＤ−６０００）で測定したところ、黒鉛の層間が２ｎｍに拡大されていることを確認することができた。また、得られた固体潤滑材の粉末を電子顕微鏡（日立（株）社製ＨＤ−２０００）で測定したところ、表面全体に酸化チタンが被覆されていることを確認することができた。 When the obtained solid lubricant powder was measured with an X-ray diffractometer (XRD-6000, manufactured by Shimadzu Corporation), it was confirmed that the graphite interlayer was enlarged to 2 nm. Moreover, when the powder of the obtained solid lubricant was measured with the electron microscope (Hitachi Co., Ltd. HD-2000), it was confirmed that the whole surface was coated with titanium oxide.
実施例３
実施例１で得た黒鉛含有スラリー溶液をろ過して黒鉛層間に硫酸分子を挿入した黒鉛−酸層間化合物を得た。この黒鉛−酸層間化合物を水１０リットルに対して１−アミノドデカン（ＡＤＣ）１００ｇ（１質量％）の混合液に投入して３０分攪拌した溶液をろ過した後、１１０℃で２時間乾燥した。乾燥後得られた塊を粉砕して平均粒径２００μｍの有機化黒鉛を回収した。粉末Ｘ線回折測定にて層間距離が３ｎｍに拡大していることを確認した。
Example 3
The graphite-containing slurry solution obtained in Example 1 was filtered to obtain a graphite-acid intercalation compound in which sulfuric acid molecules were inserted between the graphite layers. This graphite-acid intercalation compound was put into a mixed solution of 1-aminododecane (ADC) 100 g (1% by mass) with respect to 10 liters of water, and the solution stirred for 30 minutes was filtered and dried at 110 ° C. for 2 hours. . The lump obtained after drying was pulverized to recover organized graphite having an average particle size of 200 μm. It was confirmed by the powder X-ray diffraction measurement that the interlayer distance was expanded to 3 nm.
実施例４＜酸化ケイ素を層間挿入した黒鉛層間化合物にリン酸アルミニウムを被覆した固体潤滑材の創製＞
実施例１と同様にして酸化ケイ素を層間挿入した黒鉛層間化合物を作製した。次に、第一リン酸アルミニウム［純正化学社製リン酸二水素アルミニウム（一級）、形状：粉末］を蒸留水に混ぜて混合し、濃度１質量％の水溶液を調製した。
Example 4 <Creation of a solid lubricant in which aluminum phosphate is coated on a graphite intercalation compound in which silicon oxide is intercalated>
A graphite intercalation compound in which silicon oxide was intercalated was produced in the same manner as in Example 1. Next, primary aluminum phosphate [aluminum dihydrogen phosphate (primary), shape: powder] manufactured by Junsei Kagaku Co., Ltd., was mixed with distilled water and mixed to prepare an aqueous solution having a concentration of 1% by mass.
この第一リン酸アルミニウム水溶液と、上記で作製した酸化ケイ素を層間挿入してなる黒鉛層間化合物とを、質量比７：３の割合で混合し、５０℃の温度にてプロペラ式攪拌機［アズワン社製「ＰＭ−２０３」］で１時間攪拌した。 The first aluminum phosphate aqueous solution and the graphite intercalation compound formed by intercalating the silicon oxide prepared above were mixed at a mass ratio of 7: 3, and a propeller stirrer [ASONE Corporation at a temperature of 50 ° C. Stirring with “PM-203” manufactured for 1 hour.
得られた混合物を大気中、１１０℃で２４時間乾燥後解砕したのち、８００℃で３時間真空中で熱処理を実施した。熱処理後、得られた固形物を乳鉢で粉砕・分級し、目的とする固体潤滑材の粉末を得た。 The obtained mixture was dried in the atmosphere at 110 ° C. for 24 hours and then crushed, and then heat treated in vacuo at 800 ° C. for 3 hours. After the heat treatment, the obtained solid was pulverized and classified in a mortar to obtain the desired solid lubricant powder.
得られた固体潤滑材の粉末をＸ線回折装置［島津製作所社製「ＸＲＤ−６０００」］で測定したところ、黒鉛の層間が拡大されていることを確認することができた。また、得られた固体潤滑材の粉末を電子顕微鏡［日立（株）社製「ＨＤ−２０００」］で測定したところ、表面および端部にリン酸アルミニウムが被覆されていることを確認した。 When the obtained solid lubricant powder was measured with an X-ray diffractometer [“XRD-6000” manufactured by Shimadzu Corporation], it was confirmed that the graphite interlayer was enlarged. Moreover, when the obtained powder of the solid lubricant was measured with an electron microscope [“HD-2000” manufactured by Hitachi, Ltd.], it was confirmed that the surface and the end were coated with aluminum phosphate.
比較例１
未処理の天然鱗片状黒鉛（日本黒鉛社製、平均粒径５０μｍ、層間距離０．３３５４ｎｍ）を固体潤滑材として用いた。
Comparative Example 1
Untreated natural scaly graphite (manufactured by Nippon Graphite Co., Ltd., average particle size 50 μm, interlayer distance 0.3354 nm) was used as a solid lubricant.
比較例２
黒鉛材料含有スラリーに代えて、未処理の天然鱗片状黒鉛（日本黒鉛社製、平均粒径５０μｍ、層間距離０．３３５４ｎｍ）を用いた以外は、実施例１と同様にして、目的とする固体潤滑剤の粉末を得た。
Comparative Example 2
The target solid was obtained in the same manner as in Example 1 except that untreated natural scaly graphite (manufactured by Nippon Graphite Co., Ltd., average particle size 50 μm, interlayer distance 0.3354 nm) was used instead of the graphite material-containing slurry. A lubricant powder was obtained.
上記実施例１〜４および比較例１、２で得られた固体潤滑材（黒鉛試料）について、以下の条件により耐熱性を評価した。結果を表１に示す。 For the solid lubricants (graphite samples) obtained in Examples 1 to 4 and Comparative Examples 1 and 2, the heat resistance was evaluated under the following conditions. The results are shown in Table 1.
（耐熱性評価条件）
分析装置：Ｍａｃ Ｓｃｉｅｎｃｅ ２０００Ｓ社製、熱重量−示差熱分析装置 （ＴＧ−ＤＴＡ）
雰囲気 ：大気
昇温速度：１０℃／分
(Heat resistance evaluation conditions)
Analytical device: manufactured by Mac Science 2000S, thermogravimetric-differential thermal analyzer (TG-DTA)
Atmosphere: Air
Temperature increase rate: 10 ° C / min
表１より、実施例１〜実施例４で得られた黒鉛試料は、比較例１〜比較例２で得られた黒鉛試料に比べ、酸化開始温度および酸化終了温度が高いことから、耐熱性が高く、高温域においても十分な潤滑性を示すものであることが分かる。 From Table 1, since the graphite samples obtained in Examples 1 to 4 have higher oxidation start temperatures and oxidation end temperatures than the graphite samples obtained in Comparative Examples 1 to 2, the heat resistance is high. It is high and shows that it shows sufficient lubricity even in a high temperature range.
また、上記実施例１〜４および比較例１、２の黒鉛試料について、ノンアスベスト摩擦材中に添加したときの耐摩耗性評価を実施した。試験条件（ＪＡＳＯ Ｃ４０３に準拠）および摩擦材配合内容を表２、表３に示すと共に、結果を表４および図１に示す。 In addition, the graphite samples of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated for wear resistance when added to the non-asbestos friction material. The test conditions (conforming to JASO C403) and the content of the friction material are shown in Tables 2 and 3, and the results are shown in Table 4 and FIG.
表４より、実施例１〜４は比較例１、２に対し摩擦材摩耗量が減少し耐摩耗性の向上が確認できた。 From Table 4, in Examples 1-4, the friction material wear amount decreased compared with Comparative Examples 1 and 2, and it was confirmed that the wear resistance was improved.
また、実施例４（テトラエトキシシラン＋リン酸アルミニウム被覆黒鉛層間化合物）においては、実施例１（テトラエトキシシラン処理黒鉛層間化合物）に比べて、ロータ摩耗量（研削量）が減少し、ロータ研削効果を抑制することができた。 Further, in Example 4 (tetraethoxysilane + aluminum phosphate-coated graphite intercalation compound), compared with Example 1 (tetraethoxysilane-treated graphite intercalation compound), the rotor wear amount (grinding amount) is reduced, and rotor grinding is performed. The effect could be suppressed.
本発明によれば、大気中、高温域においても酸化、分解等を抑制することができ、潤滑特性を維持することができ、さらには相手材に対する研削を抑制した固体潤滑材およびその製造方法を提供することができる。 According to the present invention, a solid lubricant that can suppress oxidation, decomposition, etc. even in the atmosphere and in a high temperature range, maintain lubrication characteristics, and further suppress grinding on a counterpart material, and a method for manufacturing the same. Can be provided.
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| JP2015059142A (en) * | 2013-09-17 | 2015-03-30 | 曙ブレーキ工業株式会社 | Friction material |
| WO2016204299A1 (en) * | 2015-06-19 | 2016-12-22 | 株式会社アドヴィックス | Non-asbestos friction material |
| JP2017008167A (en) * | 2015-06-19 | 2017-01-12 | 株式会社アドヴィックス | Non-asbestos friction material |
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