JP6728769B2 - Sliding member - Google Patents
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- JP6728769B2 JP6728769B2 JP2016037715A JP2016037715A JP6728769B2 JP 6728769 B2 JP6728769 B2 JP 6728769B2 JP 2016037715 A JP2016037715 A JP 2016037715A JP 2016037715 A JP2016037715 A JP 2016037715A JP 6728769 B2 JP6728769 B2 JP 6728769B2
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- 229910052751 metal Inorganic materials 0.000 claims description 98
- 239000002184 metal Substances 0.000 claims description 98
- 239000000463 material Substances 0.000 claims description 70
- -1 alkoxide compound Chemical class 0.000 claims description 67
- 150000001875 compounds Chemical class 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 58
- 239000013522 chelant Substances 0.000 claims description 52
- 239000003575 carbonaceous material Substances 0.000 claims description 45
- 239000005011 phenolic resin Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 239000007770 graphite material Substances 0.000 claims description 19
- 125000000962 organic group Chemical group 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 125000005341 metaphosphate group Chemical group 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000010936 titanium Substances 0.000 description 35
- 229910052719 titanium Inorganic materials 0.000 description 20
- 238000012360 testing method Methods 0.000 description 13
- 230000005484 gravity Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- 239000000314 lubricant Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- NOGBEXBVDOCGDB-NRFIWDAESA-L (z)-4-ethoxy-4-oxobut-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].CCOC(=O)\C=C(\C)[O-].CCOC(=O)\C=C(\C)[O-] NOGBEXBVDOCGDB-NRFIWDAESA-L 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 description 2
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 2
- HVGAPIUWXUVICC-UHFFFAOYSA-N 6-methylheptan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)CCCCC[O-].CC(C)CCCCC[O-].CC(C)CCCCC[O-].CC(C)CCCCC[O-] HVGAPIUWXUVICC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000003332 Raman imaging Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 2
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 description 2
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 239000010457 zeolite Substances 0.000 description 2
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical group COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- LLJNVGRIQKGYCB-UHFFFAOYSA-N butyl 3-oxohexaneperoxoate;zirconium Chemical compound [Zr].CCCCOOC(=O)CC(=O)CCC.CCCCOOC(=O)CC(=O)CCC LLJNVGRIQKGYCB-UHFFFAOYSA-N 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229960001714 calcium phosphate Drugs 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 description 1
- 235000019791 dimagnesium phosphate Nutrition 0.000 description 1
- VELFFNYFZHVFNA-UHFFFAOYSA-N dioctyl phosphono phosphate Chemical group CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC VELFFNYFZHVFNA-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical group [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LZXGBBYVBJFKEL-UHFFFAOYSA-N heptatriacontanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O LZXGBBYVBJFKEL-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 1
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent 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
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 description 1
- 235000019785 monomagnesium phosphate Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Sliding-Contact Bearings (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、摺動部材に関する。 The present invention relates to a sliding member.
従来、高温高湿で潤滑成分の存在しない環境下又は水中で使用される摺動部材には、固体潤滑剤を含有した熱硬化性樹脂（例えば、特許文献１参照。）、カーボン焼結体（例えば、特許文献２参照。）等の摺動材料組成物が用いられている。これら摺動材料組成物は低摩擦性で耐摩耗性に優れる特徴を有することから、軸受、シールリング、ローター、ブレード等の摺動部材の形成に使用されている。高温高湿で潤滑成分の存在しない環境下又は水中で使用される摺動部材には、他の部品と接触する際に摩耗しにくく、摩擦係数が低いことが要求されるのに加えて、他の部品（摩擦相手材）を摩耗させないことも要求される。さらに、摺動部材は、構造上、力学的な負荷がかかる部材であることから、負荷に耐える強度を有していることが要求される。 BACKGROUND ART Conventionally, for a sliding member used in a high temperature and high humidity environment where no lubricating component is present or in water, a thermosetting resin containing a solid lubricant (for example, see Patent Document 1) and a carbon sintered body ( For example, a sliding material composition such as Patent Document 2) is used. These sliding material compositions are used for forming sliding members such as bearings, seal rings, rotors and blades because they have characteristics of low friction and excellent wear resistance. Sliding members that are used in high temperature and high humidity environments where there are no lubricating components or in water are required to have a low friction coefficient and to be less likely to wear when they come into contact with other parts. It is also required not to wear the parts (friction partner material) of. Further, since the sliding member is a member to which a mechanical load is applied structurally, it is required that the sliding member has a strength capable of withstanding the load.
また高温高湿で潤滑成分の存在しない環境下又は水中で使用される摺動部材には高い寸法安定性（低熱膨張率及び低吸湿膨潤）が求められる。寸法安定性が悪いと摺動部材と摩擦相手材との接触圧力が増大し、摩耗量が増大する恐れがある。また、摺動部材と摩擦相手材との間の接触圧力の増大に伴って摩擦力が増大しすぎると、すべり方向の動きが止まってしまう恐れがある。 Further, a sliding member used in a high temperature and high humidity environment where no lubricating component is present or in water is required to have high dimensional stability (low thermal expansion coefficient and low hygroscopic swelling). If the dimensional stability is poor, the contact pressure between the sliding member and the friction counterpart material increases, which may increase the amount of wear. Further, if the frictional force increases too much as the contact pressure between the sliding member and the friction counterpart material increases, the movement in the sliding direction may stop.
本発明は、上記問題点に鑑みてなされたものであり、寸法安定性に優れる摺動部材を提供することを目的とする。 The present invention has been made in view of the above problems, and an object thereof is to provide a sliding member having excellent dimensional stability.
前記課題を達成するための具体的手段は以下の通りである。
＜１＞ （Ａ）フェノール樹脂と、（Ｂ）炭素材料と、（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種と、を含む摺動材料組成物を用いて形成され、
前記（Ａ）フェノール樹脂の含有量が、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く前記摺動材料組成物１００質量部中に１５質量部〜３０質量部であり、
前記（Ｂ）炭素材料の含有量が、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く前記摺動材料組成物１００質量部中に６０質量部〜８５質量部であり、
前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率が、前記（Ａ）フェノール樹脂に対して３質量％〜２０質量％である摺動部材。
The specific means for achieving the above object are as follows.
<1> A sliding material composition containing (A) a phenol resin, (B) a carbon material, and (C) at least one selected from the group consisting of a metal alkoxide compound and a metal chelate compound. ,
The content of the (A) phenolic resin is 15 parts by mass to 30 parts by mass in 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound,
The content of the (B) carbon material is 60 parts by mass to 85 parts by mass in 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound,
The sliding member in which the total content of at least one selected from the group consisting of the (C) metal alkoxide compound and the metal chelate compound is 3% by mass to 20% by mass based on the (A) phenol resin.
＜２＞ 前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種に含まれる金属種が、チタンである＜１＞に記載の摺動部材。 <2> The sliding member according to <1>, wherein the metal species contained in at least one selected from the group consisting of the (C) metal alkoxide compound and the metal chelate compound is titanium.
＜３＞ 前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種が、下記式（１）〜下記式（３）からなる群より選択される少なくとも一種の化合物である＜１＞に記載の摺動部材。 <3> At least one compound selected from the group consisting of the (C) metal alkoxide compound and the metal chelate compound is at least one compound selected from the group consisting of the following formulas (1) to (3) < The sliding member according to 1>.
（式（１）〜式（３）中、Ｒ１、Ｒ２、Ｒ３及びＲ４は各々独立して、有機基を表す。） (In the formulas (1) to (3), R 1 , R 2 , R 3 and R 4 each independently represents an organic group.)
＜４＞ 前記Ｒ１、Ｒ２、Ｒ３及びＲ４で表される有機基に含まれる炭素の数が３〜１８である＜３＞に記載の摺動部材。 <4> The sliding member according to <3>, wherein the number of carbon atoms contained in the organic group represented by R 1 , R 2 , R 3 and R 4 is 3 to 18.
＜５＞ 前記（Ｂ）炭素材料が炭素質材料と黒鉛質材料とを含み、前記炭素質材料と前記黒鉛質材料との質量基準の含有比（炭素質材料／黒鉛質材料）が０．４２〜１．５である＜１＞〜＜４＞のいずれか１項に記載の摺動部材。 <5> The (B) carbon material contains a carbonaceous material and a graphite material, and the content ratio (carbonaceous material/graphite material) of the carbonaceous material and the graphite material on a mass basis is 0.42. The sliding member according to any one of <1> to <4>, which is ~1.5.
＜６＞ 前記摺動材料組成物が、（Ｄ）モース硬度が２〜６である皮膜調整材を含み、前記（Ｄ）モース硬度が２〜６である皮膜調整材の含有量が、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く前記摺動材料組成物１００質量部に対して０．３質量部〜５質量部である＜１＞〜＜５＞のいずれか１項に記載の摺動部材。 <6> The sliding material composition contains a film conditioner having (D) Mohs hardness of 2 to 6, and the content of the film conditioner having (D) Mohs hardness of 2 to 6 is as described above. C) The slide according to any one of <1> to <5>, which is 0.3 parts by mass to 5 parts by mass with respect to 100 parts by mass of the sliding material composition excluding the metal alkoxide compound and the metal chelate compound. Moving member.
＜７＞ 前記（Ｄ）モース硬度が２〜６である皮膜調整材が、ケイ酸塩、アルミノケイ酸塩、炭酸塩、リン酸塩、ポリリン酸塩、メタリン酸塩、チタン酸塩、硫酸塩及び水酸化物からなる群より選択される少なくとも一種である＜６＞に記載の摺動部材。 <7> The film conditioner having a Mohs hardness of 2 to 6 (D) is a silicate, an aluminosilicate, a carbonate, a phosphate, a polyphosphate, a metaphosphate, a titanate, a sulfate, and The sliding member according to <6>, which is at least one selected from the group consisting of hydroxides.
本発明によれば、寸法安定性に優れる摺動部材を提供することができる。 According to the present invention, it is possible to provide a sliding member having excellent dimensional stability.
以下、本発明の摺動部材を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。
本明細書において「〜」を用いて示された数値範囲には、「〜」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において組成物中の各成分の含有率又は含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本明細書において「膜」との語には、当該膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
Hereinafter, modes for carrying out the sliding member of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present specification, the numerical range indicated by using "to" includes the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another stepwise described numerical range. Good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present specification, the content rate or content of each component in the composition means that when there are a plurality of substances corresponding to each component in the composition, the plurality of substances present in the composition are present unless otherwise specified. It means the total content or content of substances.
In the present specification, the particle size of each component in the composition is a mixture of particles of the plurality of types present in the composition, unless a plurality of types of particles corresponding to each component are present in the composition, unless otherwise specified. Means a value for.
In the present specification, the term "film" refers to a case where the film is formed in a part of the region in addition to the case where the film is formed in the entire region when the region in which the film is present is observed. Is also included.
本実施形態の摺動部材は、（Ａ）フェノール樹脂と、（Ｂ）炭素材料と、（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種と、を含む摺動材料組成物を用いて形成され、前記（Ａ）フェノール樹脂の含有量が、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く前記摺動材料組成物１００質量部中に１５質量部〜３０質量部であり、前記（Ｂ）炭素材料の含有量が、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く前記摺動材料組成物１００質量部中に６０質量部〜８５質量部であり、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率が、前記（Ａ）フェノール樹脂に対して３質量％〜２０質量％である。 The sliding member of the present embodiment is a sliding material composition containing (A) a phenol resin, (B) a carbon material, and (C) at least one selected from the group consisting of a metal alkoxide compound and a metal chelate compound. The content of the (A) phenol resin is 15 to 30 parts by mass in 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound. The content of the (B) carbon material is 60 parts by mass to 85 parts by mass in 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound, and the (C ) The total content of at least one selected from the group consisting of a metal alkoxide compound and a metal chelate compound is 3% by mass to 20% by mass based on the (A) phenol resin.
本実施形態によれば、寸法安定性に優れる摺動部材を提供することができる。本実施形態の摺動部材が寸法安定性に優れる理由は明確ではないが、以下のように推察される。
摺動部材における吸湿の起点はフェノール樹脂に含まれる水酸基と考えられる。摺動部材に含まれる水酸基の量が多いと親水性が高くなるため、空気中に存在する水分を吸収しやすく、膨潤により摺動部材の寸法が増大することがある。ここで、金属アルコキシド化合物及び金属キレート化合物は、水酸基、カルボキシル基、エポキシ基等の官能基と反応することができる。本実施形態では、金属アルコキシド化合物及び金属キレート化合物がフェノール樹脂に含まれる水酸基と反応し、「Ｏ−金属元素−Ｏ」結合からなる架橋点を形成することができる。「Ｏ−金属元素−Ｏ」結合が形成されることで、摺動部材に含まれる水酸基の量が減少する。そのため摺動部材の親水性を低下させ、吸収する水分量を削減することができ、吸湿膨潤による摺動部材の寸法変化を抑制できると推察される。
また、「Ｏ−金属元素−Ｏ」結合の架橋点が形成されることで摺動部材の架橋密度が向上する。その結果、「Ｏ−金属元素−Ｏ」結合の架橋点が形成されていない摺動部材に比較して、「Ｏ−金属元素−Ｏ」結合の架橋点が形成されている摺動部材は、同じ吸湿量であっても膨潤がより抑制されると推察される。
According to this embodiment, it is possible to provide a sliding member having excellent dimensional stability. The reason why the sliding member of the present embodiment is excellent in dimensional stability is not clear, but it is presumed as follows.
The starting point of moisture absorption in the sliding member is considered to be a hydroxyl group contained in the phenol resin. If the amount of hydroxyl groups contained in the sliding member is large, the hydrophilicity becomes high, so that the water present in the air is easily absorbed, and the dimension of the sliding member may increase due to swelling. Here, the metal alkoxide compound and the metal chelate compound can react with a functional group such as a hydroxyl group, a carboxyl group, and an epoxy group. In the present embodiment, the metal alkoxide compound and the metal chelate compound can react with the hydroxyl group contained in the phenol resin to form a cross-linking point composed of an “O-metal element-O” bond. The formation of the "O-metal element-O" bond reduces the amount of hydroxyl groups contained in the sliding member. Therefore, it is presumed that the hydrophilicity of the sliding member can be lowered, the amount of water absorbed can be reduced, and the dimensional change of the sliding member due to moisture swelling can be suppressed.
Further, the cross-linking density of the sliding member is improved by forming the cross-linking point of the "O-metal element-O" bond. As a result, as compared with the sliding member in which the cross-linking point of the “O-metal element-O” bond is not formed, the sliding member in which the cross-linking point of the “O-metal element-O” bond is formed is It is presumed that swelling is further suppressed even with the same moisture absorption amount.
以下、本実施形態の摺動部材の形成に用いられる摺動材料組成物について説明する。
本実施形態に係る摺動材料組成物は、（Ａ）フェノール樹脂と、（Ｂ）炭素材料と、（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種と、を含む。本実施形態に係る摺動材料組成物は、必要に応じてその他の成分を含んでいてもよい。
Hereinafter, the sliding material composition used for forming the sliding member of the present embodiment will be described.
The sliding material composition according to the present embodiment includes (A) a phenol resin, (B) a carbon material, and (C) at least one selected from the group consisting of a metal alkoxide compound and a metal chelate compound. The sliding material composition according to the present embodiment may include other components as necessary.
（フェノール樹脂）
本実施形態に係る摺動材料組成物は、（Ａ）フェノール樹脂を含有する。本実施形態に係る摺動材料組成物に含まれる（Ａ）フェノール樹脂の含有量は、（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く摺動材料組成物１００質量部中に１５質量部〜３０質量部とされる。（Ａ）フェノール樹脂の含有量を１５質量部〜３０質量部の範囲とすることで、カーボン焼結体よりも強度に優れた摺動部材を提供できる。
（Ａ）フェノール樹脂の含有量は、曲げ強さを向上する観点から２３質量部〜３０質量部であることが好ましい。一方、（Ａ）フェノール樹脂の含有量は、寸法安定性を向上する観点から１０質量部〜２７質量部であることが好ましく、１５質量部〜２７質量部であることがより好ましい。したがって、（Ａ）フェノール樹脂の含有量は、曲げ強さと寸法安定性の両者を向上する観点から、２３質量部〜２７質量部であることがより好ましい。
(Phenolic resin)
The sliding material composition according to the present embodiment contains (A) a phenol resin. The content of the (A) phenol resin contained in the sliding material composition according to the present embodiment is 15 parts by mass to 30 parts by mass in 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound. It is considered to be part by mass. By setting the content of the (A) phenolic resin in the range of 15 parts by mass to 30 parts by mass, it is possible to provide a sliding member having higher strength than the carbon sintered body.
The content of the (A) phenolic resin is preferably 23 parts by mass to 30 parts by mass from the viewpoint of improving bending strength. On the other hand, the content of the (A) phenolic resin is preferably 10 parts by mass to 27 parts by mass, and more preferably 15 parts by mass to 27 parts by mass, from the viewpoint of improving dimensional stability. Therefore, the content of the (A) phenol resin is more preferably 23 parts by mass to 27 parts by mass from the viewpoint of improving both bending strength and dimensional stability.
本実施形態で用いる（Ａ）フェノール樹脂としては、例えば、ノボラック型フェノール樹脂及びレゾール型フェノール樹脂が挙げられる。本実施形態においては、（Ａ）フェノール樹脂を１種単独で使用してもよく、２種以上を併用してもよい。 Examples of the (A) phenol resin used in the present embodiment include novolac type phenol resin and resol type phenol resin. In the present embodiment, the phenol resin (A) may be used alone or in combination of two or more.
（炭素材料）
本実施形態に係る摺動材料組成物は、（Ｂ）炭素材料を含有する。本実施形態に係る摺動材料組成物に含まれる（Ｂ）炭素材料の含有量は、（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く摺動材料組成物１００質量部中に６０質量部〜８５質量部とされる。
摺動部材は、摩擦相手材と同程度の熱膨張係数（寸法安定性）を有するように調整されることが好ましい。（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く摺動材料組成物１００質量部中に、（Ｂ）炭素材料を６０質量部〜８５質量部含むことで、耐摩耗性及び寸法安定性に優れる摺動部材を得ることができる。特に、高温高湿で潤滑成分の存在しない環境下又は水中において優れた寸法安定性が得られる。そのため、より寸法精度が求められる構造部材に使用可能な摺動部材が得られる。また、より長寿命な摺動部材を提供できる。さらには、高温時に摺動部材の摩擦係数が急激に増大することを防ぐことができる。
（Ｂ）炭素材料の含有量は、寸法安定性の観点からは、６５質量部〜８０質量部であることが好ましい。一方、（Ｂ）炭素材料の含有量は、強度及び摺動部材を形成する際の摺動材料組成物の流動性の観点からは、６０質量部〜７５質量部であることが好ましい。したがって、（Ｂ）炭素材料の含有量は、寸法安定性、強度及び摺動部材を形成する際の摺動材料組成物の流動性の観点からは、６５質量部〜７５質量部であることがより好ましい。
(Carbon material)
The sliding material composition according to the present embodiment contains (B) a carbon material. The content of the (B) carbon material contained in the sliding material composition according to the present embodiment is 60 parts by mass to 85 parts by mass per 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound. It is considered to be part by mass.
The sliding member is preferably adjusted so as to have a thermal expansion coefficient (dimensional stability) similar to that of the friction counterpart material. By including 60 parts by mass to 85 parts by mass of the (B) carbon material in 100 parts by mass of the sliding material composition (C) excluding the metal alkoxide compound and the metal chelate compound, a sliding material having excellent wear resistance and dimensional stability. A moving member can be obtained. In particular, excellent dimensional stability can be obtained in an environment of high temperature and high humidity without a lubricating component or in water. Therefore, it is possible to obtain a sliding member that can be used as a structural member that requires higher dimensional accuracy. Moreover, a sliding member having a longer life can be provided. Furthermore, it is possible to prevent the friction coefficient of the sliding member from rapidly increasing at high temperatures.
The content of the (B) carbon material is preferably 65 parts by mass to 80 parts by mass from the viewpoint of dimensional stability. On the other hand, the content of the (B) carbon material is preferably 60 parts by mass to 75 parts by mass from the viewpoint of strength and fluidity of the sliding material composition when forming the sliding member. Therefore, the content of the (B) carbon material is from 65 parts by mass to 75 parts by mass from the viewpoint of dimensional stability, strength, and fluidity of the sliding material composition when forming the sliding member. More preferable.
（Ｂ）炭素材料は、炭素質材料と黒鉛質材料とに大別される。炭素質材料と黒鉛質材料とは、結晶性の度合いで区別される。
炭素質材料としては、コークス、カーボンブラック、活性炭、石炭、木炭等が挙げられる。黒鉛質材料としては、天然黒鉛及び人造黒鉛が挙げられる。本実施形態では、価格、品質の安定性等の観点から、炭素質材料としてはコークスを用いることが好ましく、黒鉛質材料としては人造黒鉛を用いることが好ましい。
(B) Carbon materials are roughly classified into carbonaceous materials and graphite materials. A carbonaceous material and a graphite material are distinguished by the degree of crystallinity.
Examples of the carbonaceous material include coke, carbon black, activated carbon, coal and charcoal. Examples of the graphite material include natural graphite and artificial graphite. In the present embodiment, it is preferable to use coke as the carbonaceous material, and it is preferable to use artificial graphite as the graphite material from the viewpoints of price, quality stability, and the like.
本実施形態において、炭素材料の結晶性の度合いは、ラマンイメージング測定による測定結果に基づいて判断できる。通常、炭素材料のラマンスペクトルには、１３００ｃｍ−１〜１４００ｃｍ−１の範囲に非晶質構造に帰属されるピーク（Ｉｄ）と、１５３０ｃｍ−１〜１６３０ｃｍ−１の範囲に黒鉛結晶構造に帰属されるピーク（Ｉｇ）が観察される。両ピークの強度比Ｉｄ／ＩｇをＲ値とし、Ｒ値が０．５以上である場合に炭素質材料と判断できる。一方、Ｒ値が０．５未満である場合に黒鉛質材料と判断できる。
ラマンイメージング測定は、例えばＴｈｅｒｍｏＦｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製顕微レーザーラマン分光装置（ＤＸＲ Ｒａｍａｎ ｍｉｃｒｏｓｃｏｐｅ）を用いて測定することができる。
In the present embodiment, the degree of crystallinity of the carbon material can be determined based on the measurement result by Raman imaging measurement. Usually, the Raman spectrum of the carbon material, the peak (Id) which is attributable to amorphous structure in a range of 1300cm -1 ~1400cm -1, is assigned to a graphite crystal structure in the range of 1530cm -1 ~1630cm -1 Peak (Ig) is observed. The intensity ratio Id/Ig of both peaks is defined as an R value, and when the R value is 0.5 or more, it can be determined as a carbonaceous material. On the other hand, when the R value is less than 0.5, it can be judged as a graphite material.
The Raman imaging measurement can be performed using, for example, a microscopic laser Raman spectroscope (DXR Raman microscope) manufactured by ThermoFisher Scientific.
本実施形態において、（Ｂ）炭素材料の平均粒径は、５μｍ〜１００μｍであることが好ましく、１０μｍ〜６０μｍであることがより好ましく、１５μｍ〜４０μｍであることが更に好ましい。なお、本実施形態において、平均粒径は、レーザー回折法によって測定した粒度の体積累積分布（％）において、粒子径の小さい方から積算して５０％となるときの粒子径Ｄ５０（μｍ）をいう。 In the present embodiment, the average particle size of the (B) carbon material is preferably 5 μm to 100 μm, more preferably 10 μm to 60 μm, and further preferably 15 μm to 40 μm. In the present embodiment, the average particle size is a particle size D 50 (μm) when the cumulative particle size distribution (%) measured by a laser diffraction method is 50% by adding from the smaller particle size. Say.
本実施形態の摺動部材は、その最表面を摩擦相手材に接触させて使用することができる。本実施形態の摺動部材は、摩耗した際に発生する摩耗粉が摺動部材の摩擦相手材との接触面及び摩擦相手材の摺動部材との接触面に付着し、摺動部材と摩擦相手材との間に皮膜を形成することで、耐摩耗性を発現する。摩耗粉の付着量が少なすぎることがなく皮膜の厚みを確保できれば十分な耐摩耗性が得られる傾向にある。
摺動部材と摩擦相手材との間に形成される皮膜の厚みは、例えば、（Ｂ）炭素材料の組成により調整することができる。
The sliding member of the present embodiment can be used by bringing its outermost surface into contact with the friction partner material. In the sliding member of the present embodiment, abrasion powder generated when worn adheres to the contact surface of the sliding member with the friction mating member and the contact surface of the friction mating member with the sliding member to cause friction with the sliding member. Abrasion resistance is exhibited by forming a film between the mating material. Sufficient wear resistance tends to be obtained if the thickness of the film can be secured without the adhesion amount of wear powder being too small.
The thickness of the film formed between the sliding member and the friction counterpart material can be adjusted, for example, by the composition of the (B) carbon material.
（Ｂ）炭素材料が炭素質材料と黒鉛質材料とを含む場合に、炭素質材料と黒鉛質材料との質量基準の含有比（炭素質材料／黒鉛質材料）が小さい、つまり黒鉛質材料が多い場合では、摺動部材の摩擦相手材との接触面及び摩擦相手材の摺動部材との接触面に摩耗粉が付着しやすいため、皮膜の厚みが増大する傾向にある。また、黒鉛質材料が多いと摺動部材の強度が低下する傾向にある。一方、含有比（炭素質材料／黒鉛質材料）が大きい、つまり炭素質材料が多い場合では、摺動部材の摩擦相手材との接触面及び摩擦相手材の摺動部材との接触面への摩耗粉の付着しやすさが低下し、皮膜厚みが薄くなる傾向にある。また、炭素質材料が多いと、摺動部材の強度が向上する傾向にある。
そのため、本実施形態では、（Ｂ）炭素材料が炭素質材料と黒鉛質材料とを含む場合に、含有比（炭素質材料／黒鉛質材料）を０．４２〜１．５（質量比）とすることで、皮膜の厚みが最適化され、摺動部材の優れた耐摩耗性及び強度を発現できる。摺動部材の強度を向上する観点からは、含有比（炭素質材料／黒鉛質材料）が０．６０〜１．５（質量比）であることが好ましく、摩擦係数を低くする観点からは、含有比（炭素質材料／黒鉛質材料）が０．４２〜０．８０（質量比）であることが好ましい。摩耗粉の付着性の制御による皮膜厚みの最適化、強度及び耐摩耗性の総合的な観点からは含有比（炭素質材料／黒鉛質材料）は０．６０〜０．８０であることがより好ましい。
(B) When the carbon material contains a carbonaceous material and a graphite material, the content ratio (carbonaceous material/graphite material) on the mass basis of the carbonaceous material and the graphite material is small, that is, the graphite material is In many cases, abrasion powder tends to adhere to the contact surface of the sliding member with the friction partner material and the contact surface of the friction partner material with the sliding member, so that the thickness of the coating tends to increase. Further, if the amount of the graphite material is large, the strength of the sliding member tends to decrease. On the other hand, when the content ratio (carbonaceous material/graphite material) is large, that is, when there are many carbonaceous materials, the contact surface of the sliding member with the friction partner material and the contact surface of the friction partner material with the sliding member are There is a tendency that the adhesion of abrasion powder is reduced and the film thickness is reduced. Further, when the amount of carbonaceous material is large, the strength of the sliding member tends to be improved.
Therefore, in the present embodiment, when the carbon material (B) contains a carbonaceous material and a graphite material, the content ratio (carbonaceous material/graphite material) is 0.42 to 1.5 (mass ratio). By doing so, the thickness of the film is optimized, and the excellent wear resistance and strength of the sliding member can be exhibited. From the viewpoint of improving the strength of the sliding member, the content ratio (carbonaceous material/graphitic material) is preferably 0.60 to 1.5 (mass ratio), and from the viewpoint of reducing the friction coefficient, The content ratio (carbonaceous material/graphitic material) is preferably 0.42 to 0.80 (mass ratio). It is more preferable that the content ratio (carbonaceous material/graphitic material) is 0.60 to 0.80 from the viewpoint of optimizing the film thickness by controlling the adhesion of abrasion powder, and comprehensively considering strength and abrasion resistance. preferable.
（金属アルコキシド化合物及び金属キレート化合物）
本実施形態に係る摺動材料組成物は、（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種を含有する。本実施形態に係る摺動材料組成物に含まれる（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率は、（Ａ）フェノール樹脂に対して３質量％〜２０質量％とされる。（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率を（Ａ）フェノール樹脂に対して３質量％〜２０質量％の範囲とすることで、（Ａ）フェノール樹脂の吸湿を抑制し、吸湿による摺動部材の寸法の増加を抑制することができる。これにより、例えば、８５℃８５％ＲＨの環境下において３３６時間放置後でも５ｍｍ幅の摺動部材の寸法増加率を０．２％以下とすることが可能となる傾向にあり、寸法安定性に優れる摺動部材が提供できる。そのため、高温高湿で潤滑成分の存在しない環境下又は水中において好適に使用される摺動部材が提供できる。
（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率が３質量％以上であれば、十分な吸湿抑制効果が得られ、寸法安定性が向上する傾向にある。また、（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率が２０質量％以下であれば、摺動部材の強度が向上するか、又は十分な吸湿抑制効果が得られ、寸法安定性が向上する傾向にある。
摺動部材の吸湿抑制効果を達成し、寸法安定性を向上するためには、（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率は、（Ａ）フェノール樹脂に対して５質量％〜１８質量％であることが好ましく、１０質量％〜１５質量％であることがより好ましい。
(Metal alkoxide compound and metal chelate compound)
The sliding material composition according to the present embodiment contains at least one selected from the group consisting of (C) metal alkoxide compound and metal chelate compound. The total content of at least one selected from the group consisting of (C) metal alkoxide compounds and metal chelate compounds contained in the sliding material composition according to the present embodiment is 3% by mass relative to (A) phenol resin. ˜20% by mass. (C) By setting the total content of at least one selected from the group consisting of a metal alkoxide compound and a metal chelate compound in the range of 3% by mass to 20% by mass with respect to the (A) phenol resin, (A) It is possible to suppress the moisture absorption of the phenol resin and to suppress the increase in the dimension of the sliding member due to the moisture absorption. As a result, for example, even after being left for 336 hours in an environment of 85° C. and 85% RH, the dimensional increase rate of the sliding member having a width of 5 mm tends to be 0.2% or less. An excellent sliding member can be provided. Therefore, it is possible to provide a sliding member that is preferably used in an environment where high temperature and high humidity do not contain a lubricating component or in water.
(C) If the total content of at least one selected from the group consisting of a metal alkoxide compound and a metal chelate compound is 3% by mass or more, a sufficient moisture absorption suppressing effect is obtained, and dimensional stability tends to be improved. is there. Further, if the total content of at least one selected from the group consisting of (C) metal alkoxide compound and metal chelate compound is 20 mass% or less, the strength of the sliding member is improved or sufficient moisture absorption is suppressed. The effect is obtained, and the dimensional stability tends to be improved.
In order to achieve the moisture absorption suppressing effect of the sliding member and improve the dimensional stability, the total content of at least one selected from the group consisting of (C) metal alkoxide compound and metal chelate compound is (A) It is preferably 5% by mass to 18% by mass, and more preferably 10% by mass to 15% by mass, relative to the phenol resin.
金属アルコキシド化合物としては、アルミニウム、チタン、ジルコニウム等の金属アルコキシド化合物が挙げられる。金属キレート化合物としては、アセト酢酸等がアルミニウム、チタン、ジルコニウム等の金属に配位した金属キレート化合物が挙げられる。
本実施形態では、金属アルコキシド化合物又は金属キレート化合物に含まれる金属種に特に限定はない。市販されている種類が多いという観点から、金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種に含まれる金属種が、チタンであることが好ましい。すなわち、金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種が、チタンアルコキシド化合物及びチタンキレート化合物からなる群より選択される少なくとも一種であることが好ましい。
Examples of the metal alkoxide compound include metal alkoxide compounds such as aluminum, titanium and zirconium. Examples of the metal chelate compound include metal chelate compounds in which acetoacetic acid and the like are coordinated with metals such as aluminum, titanium, and zirconium.
In the present embodiment, the metal species contained in the metal alkoxide compound or metal chelate compound is not particularly limited. From the viewpoint that many types are commercially available, it is preferable that the metal species contained in at least one selected from the group consisting of metal alkoxide compounds and metal chelate compounds is titanium. That is, at least one selected from the group consisting of metal alkoxide compounds and metal chelate compounds is preferably at least one selected from the group consisting of titanium alkoxide compounds and titanium chelate compounds.
（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種は、下記式（１）〜下記式（３）からなる群より選択される少なくとも一種の化合物であることも好ましい。（Ｃ）金属アルコキシド化合物及び金属キレート化合物は、１種単独で用いても、２種以上を併用してもよい。（Ｃ）金属アルコキシド化合物及び金属キレート化合物を２種以上併用する場合、各化合物に含まれる金属種は同じであっても異なっていてもよい。 At least one selected from the group consisting of (C) a metal alkoxide compound and a metal chelate compound is also preferably at least one compound selected from the group consisting of the following formulas (1) to (3). The (C) metal alkoxide compound and metal chelate compound may be used alone or in combination of two or more. When two or more (C) metal alkoxide compounds and metal chelate compounds are used in combination, the metal species contained in each compound may be the same or different.
式（１）〜式（３）中、Ｒ１、Ｒ２、Ｒ３及びＲ４は各々独立して、有機基を表す。Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ同じであっても異なるものであってもよい。 In formulas (1) to (3), R 1 , R 2 , R 3 and R 4 each independently represent an organic group. R 1 , R 2 , R 3 and R 4 may be the same or different.
ここで、式（１）で表される化合物はチタンアルコキシド化合物又はチタンキレート化合物であり、式（２）で表される化合物はジルコニウムアルコキシド化合物又はジルコニウムキレート化合物であり、式（３）で表される化合物はアルミニウムアルコキシド化合物又はアルミニウムキレート化合物である。 Here, the compound represented by the formula (1) is a titanium alkoxide compound or a titanium chelate compound, and the compound represented by the formula (2) is a zirconium alkoxide compound or a zirconium chelate compound, represented by the formula (3). The compound is an aluminum alkoxide compound or an aluminum chelate compound.
式（１）〜式（３）中、Ｒ１、Ｒ２、Ｒ３及びＲ４で表される有機基は、有機基に含まれる炭素の数が小さいと反応性が早く、架橋密度がより高くなることが期待できる。また、有機基に含まれる炭素の数が大きいと（Ｃ）金属アルコキシド化合物又は金属キレート化合物自身の疎水性が高くなり、摺動部材の吸湿量がより低減することが期待できる。そのため、Ｒ１、Ｒ２、Ｒ３及びＲ４で表される有機基に含まれる炭素の数は、３〜１８であることが好ましく、架橋密度の観点からは３〜８であることがより好ましく、疎水性の観点からは５〜１８であることがより好ましい。Ｒ１、Ｒ２、Ｒ３及びＲ４で表される有機基に含まれる炭素の数は、更に好ましくは６〜１０であり、８であることが特に好ましい。 In the formulas (1) to (3), the organic groups represented by R 1 , R 2 , R 3 and R 4 have high reactivity when the number of carbons contained in the organic group is small, and the crosslink density is higher. It can be expected to be higher. Further, if the number of carbons contained in the organic group is large, the hydrophobicity of the (C) metal alkoxide compound or the metal chelate compound itself becomes high, and it can be expected that the moisture absorption amount of the sliding member is further reduced. Therefore, the number of carbon atoms contained in the organic group represented by R 1 , R 2 , R 3 and R 4 is preferably 3 to 18, and more preferably 3 to 8 from the viewpoint of crosslinking density. It is more preferably 5 to 18 from the viewpoint of hydrophobicity. The number of carbon atoms contained in the organic group represented by R 1 , R 2 , R 3 and R 4 is more preferably 6 to 10 and particularly preferably 8.
Ｒ１、Ｒ２、Ｒ３及びＲ４で表される有機基としては、アルキル基、アリール基、シクロアルキル基等が挙げられる。また、Ｒ１、Ｒ２、Ｒ３及びＲ４で表される有機基のうちの２つが互いに結合して、Ｔｉ、Ｚｒ又はＡｌ原子を含む環構造を形成していてもよい。
アルキル基は、直鎖状であっても分岐鎖状であってもよい。アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、２−エチルヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等が挙げられる。アルキル基は、フッ素、塩素、臭素等のハロゲン原子、水酸基、カルボキシル基などで置換されていてもよい。
アリール基の具体例としては、フェニル基、ナフチル基等が挙げられる。アリール基は、フッ素、塩素、臭素等のハロゲン原子、水酸基、カルボキシル基、アルキル基などで置換されていてもよい。
シクロアルキル基の具体例としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。シクロアルキル基は、フッ素、塩素、臭素等のハロゲン原子、水酸基、カルボキシル基、アルキル基などで置換されていてもよい。
Ｒ１、Ｒ２、Ｒ３及びＲ４で表される有機基のうちの２つが互いに結合して、Ｔｉ、Ｚｒ又はＡｌ原子を含む環構造を形成する場合の具体例としては、１，２−エタンジオキシ基、１，３−プロパンジオキシ基、１，４−ブタンジオキシ基、−ＯＣＯＣＨ２Ｏ−基（グリコール酸由来の基）等が挙げられる。
Examples of the organic group represented by R 1 , R 2 , R 3 and R 4 include an alkyl group, an aryl group and a cycloalkyl group. Two of the organic groups represented by R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring structure containing a Ti, Zr or Al atom.
The alkyl group may be linear or branched. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group. Group, nonyl group, decyl group and the like. The alkyl group may be substituted with a halogen atom such as fluorine, chlorine or bromine, a hydroxyl group or a carboxyl group.
Specific examples of the aryl group include a phenyl group and a naphthyl group. The aryl group may be substituted with a halogen atom such as fluorine, chlorine or bromine, a hydroxyl group, a carboxyl group or an alkyl group.
Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. The cycloalkyl group may be substituted with a halogen atom such as fluorine, chlorine or bromine, a hydroxyl group, a carboxyl group or an alkyl group.
Specific examples of the case where two of the organic groups represented by R 1 , R 2 , R 3 and R 4 are bonded to each other to form a ring structure containing a Ti, Zr or Al atom are: Examples thereof include an ethanedioxy group, a 1,3-propanedioxy group, a 1,4-butanedioxy group, and an —OCOCH 2 O— group (a group derived from glycolic acid).
また、−ＯＲ１、−ＯＲ２、−ＯＲ３及び−ＯＲ４で表される基としては、アセタト基；アセチルアセトナト基；メチルアセトアセタト基、エチルアセトアセタト基等のアルキルアセトアセタト基；ステアリル基、イソステアリル基等のカルボキシル基を含む化合物におけるカルボキシル基から水素原子を除いた基；ジオクチルパイロホスフェート基等のピロリン酸化合物におけるピロリン酸基から水素原子を除いた基；ドデシルベンゼンスルホン酸基等のスルホン酸化合物におけるスルホン酸基から水素原子を除いた基などが挙げられる。 The groups represented by —OR 1 , —OR 2 , —OR 3 and —OR 4 include an acetato group; an acetylacetonato group; an alkylacetoacetato group such as a methylacetoacetate group and an ethylacetoacetato group. Group; a group in which a hydrogen atom is removed from a carboxyl group in a compound containing a carboxyl group such as stearyl group and isostearyl group; a group in which a hydrogen atom is removed from a pyrophosphate group in a pyrophosphate compound such as a dioctylpyrophosphate group; dodecylbenzenesulfone Examples thereof include a group obtained by removing a hydrogen atom from a sulfonic acid group in a sulfonic acid compound such as an acid group.
上記式（１）で表されるチタンアルコキシド化合物又はチタンキレート化合物としては、マツモトファインケミカル株式会社から市販されているオルガチックス（登録商標）シリーズのオルガチックスＴＡ−１０（チタンテトライソプロポキシド［Ｔｉ（Ｏ−ｉ−Ｃ３Ｈ７）４］）、オルガチックスＴＡ−２１（チタンテトラノルマルブトキシド［Ｔｉ（Ｏ−ｎ−Ｃ４Ｈ９）４］）、オルガチックスＴＡ−３０（チタンテトラ−２−エチルヘキソキシド［Ｔｉ（ＯＣ８Ｈ１７）４］）、オルガチックスＴＣ−１００（チタンジイソプロポキシビス（アセチルアセトネート）［Ｔｉ（Ｏ−ｉ−Ｃ３Ｈ７）２（Ｃ５Ｈ７Ｏ２）２］）、オルガチックスＴＣ−４０１（チタンテトラアセチルアセトネート［Ｔｉ（Ｃ５Ｈ７Ｏ２）４］）、オルガチックスＴＣ−２０１（チタニウムジ−２−エチルヘキソキシビス（２−エチル−３−ヒドロキシヘキソキシド）［Ｔｉ（ＯＣ８Ｈ１７）２（Ｃ８Ｈ１７Ｏ２）２］）、オルガチックスＴＣ−７５０（チタンジイソプロポキシビス（エチルアセトアセテート）［Ｔｉ（Ｏ−ｉ−Ｃ３Ｈ７）２（Ｃ６Ｈ９Ｏ３）２］）、オルガチックスＴＣ−７３０（チタン−１，３−プロパンジオキシビス（エチルアセトアセテート）［Ｔｉ（Ｃ３Ｈ６Ｏ２）２（Ｃ６Ｈ９Ｏ３）２］）、オルガチックスＴＣ−８００（チタンイソステアレート［Ｔｉ（Ｏ−ｉ−Ｃ３Ｈ７）（ＯＣＯＣ１７Ｈ３５）３］）、オルガチックスＴＣ−２２０（チタンオクチレングリコレート化合物）、オルガチックスＴＣ−１０４０（リン酸チタン化合物）等が挙げられる。
また、上記式（１）で表されるチタンアルコキシド化合物又はチタンキレート化合物としては、味の素ファインテクノ株式会社から市販されているプレンアクト（登録商標）シリーズのプレンアクトＫＲ ＴＴＳ（イソプロピルトリイソステアロイルチタネート）、プレンアクトＫＲ３８Ｓ（イソプロピルトリス（ジオクチルパイロホスフェート）チタネート）、プレンアクトＫＲ１３８Ｓ（ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート）、プレンアクトＫＲ２３８Ｓ（トリス（ジオクチルパイロホスフェート）エチレンチタネート）、プレンアクトＫＲ３３８Ｘ（イソプロピルジオクチルパイロホスフェートチタネート）、プレンアクトＫＲ９ＳＡ（イソプロピルトリス（ドデシルベンゼンスルフォニル）チタネート）等が挙げられる。
As the titanium alkoxide compound or titanium chelate compound represented by the above formula (1), Organix TA-10 (titanium tetraisopropoxide [Ti( O-i-C 3 H 7 ) 4]), Orgatics TA-21 (titanium tetra-n-butoxide [Ti (O-n-C 4 H 9) 4]), Orgatics TA-30 (titanium tetra-2 ethylhexoxide [Ti (OC 8 H 17) 4]), Orgatix TC-100 (titanium diisopropoxy bis (acetylacetonate) [Ti (O-i- C 3 H 7) 2 (C 5 H 7 O 2 ) 2 ]), Organix TC-401 (titanium tetraacetylacetonate [Ti(C 5 H 7 O 2 ) 4 ]), Organix TC-201 (titanium di-2-ethylhexoxybis(2- ethyl-3-hydroxy-hexoxide) [Ti (OC 8 H 17 ) 2 (C 8 H 17 O 2) 2]), Orgatix TC-750 (titanium diisopropoxy bis (ethylacetoacetate) [Ti (O -i-C 3 H 7) 2 (C 6 H 9 O 3) 2]), Orgatix TC-730 (titanium-1,3-dioxy-bis (ethylacetoacetate) [Ti (C 3 H 6 O 2) 2 (C 6 H 9 O 3) 2]), Orgatix TC-800 (titanium isostearate [Ti (O-i-C 3 H 7) (OCOC 17 H 35) 3]), Orgatix TC -220 (titanium octylene glycolate compound), Organix TC-1040 (titanium phosphate compound) and the like can be mentioned.
Further, as the titanium alkoxide compound or the titanium chelate compound represented by the above formula (1), Planeact KR TTS (isopropyl triisostearoyl titanate) of Planeact (registered trademark) series commercially available from Ajinomoto Fine-Techno Co., Inc. KR38S (isopropyl tris(dioctyl pyrophosphate) titanate), preneact KR138S (bis(dioctyl pyrophosphate)oxyacetate titanate), preneact KR238S (tris(dioctyl pyrophosphate)ethylene titanate), preneact KR338X(isopropyl dioctyl pyrophenate phosphate) KR9SA (isopropyl tris(dodecylbenzenesulfonyl) titanate) and the like can be mentioned.
上記式（２）で表されるジルコニウムアルコキシド化合物又はジルコニウムキレート化合物としては、例えば、マツモトファインケミカル株式会社から市販されているオルガチックス（登録商標）シリーズのオルガチックスＺＡ−４５（ジルコニウムテトラノルマルプロポキシド［Ｚｒ（Ｏ−ｎ−Ｃ３Ｈ７）４］）、ＺＡ−６５（ジルコニウムテトラノルマルブトキシド［Ｚｒ（Ｏ−ｎ−Ｃ４Ｈ９）４］）、ＺＣ−１５０（ジルコニウムテトラアセチルアセトネート［Ｚｒ（Ｃ５Ｈ７Ｏ２）４］）、ＺＣ−５４０（ジルコニウムトリブトキシモノアセチルアセトネート［Ｚｒ（Ｏ−ｎ−Ｃ４Ｈ９）３（Ｃ５Ｈ７Ｏ２）］）、ＺＣ−５８０（ジルコニウムジブトキシビス（エチルアセトアセテート）［Ｚｒ（Ｏ−ｎ−Ｃ４Ｈ９）２（Ｃ６Ｈ９Ｏ３）２］）、ＺＣ−３２０（ステアリン酸ジルコニウム［Ｚｒ（Ｏ−ｎ−Ｃ４Ｈ９）３（ＯＣＯＣ１７Ｈ３５）］）等が挙げられる。 Examples of the zirconium alkoxide compound or the zirconium chelate compound represented by the above formula (2) include, for example, Organix (registered trademark) series ZA-45 (zirconium tetranormal propoxide [commercially available from Matsumoto Fine Chemical Co., Ltd. Zr (O-n-C 3 H 7) 4]), ZA-65 ( zirconium tetra-n-butoxide [Zr (O-n-C 4 H 9) 4]), ZC-150 ( zirconium tetra acetylacetonate [Zr (C 5 H 7 O 2) 4]), ZC-540 ( zirconium tributoxy monoacetylacetonate [Zr (O-n-C 4 H 9) 3 (C 5 H 7 O 2)]), ZC-580 (zirconium dibutoxy bis (ethylacetoacetate) [Zr (O-n- C 4 H 9) 2 (C 6 H 9 O 3) 2]), ZC-320 ( zirconium stearate [Zr (O-n-C 4 H 9 ) 3 (OCOC 17 H 35 )]) and the like.
上記式（３）で表されるアルミニウムアルコキシド化合物又はアルミニウムキレート化合物としては、アルミニウムイソプロポキシド［Ａｌ（Ｏ−ｉ−Ｃ３Ｈ７）３］、味の素ファインテクノ株式会社から市販されているプレンアクト（登録商標）シリーズのプレンアクトＫＲ ＡＬ−Ｍ（アルキルアセトアセテートアルミニウムジイソプロピレート）等が挙げられる。 The above formula (3) alkoxide compound represented by or aluminum chelate compounds, aluminum isopropoxide [Al (O-i-C 3 H 7) 3], which is commercially available from Ajinomoto Fine-Techno Co. Plenact ( (Registered trademark) series Plenact KR AL-M (alkyl acetoacetate aluminum diisopropylate) and the like.
（皮膜調整材）
本実施形態に係る摺動材料組成物は、（Ｄ）モース硬度が２〜６である皮膜調整材（以下、特定皮膜調整材と称することがある。）を含有してもよい。本実施形態に係る摺動材料組成物に特定皮膜調整材を添加することで、摩耗粉により形成される皮膜を削る効果が発現し、皮膜の厚みを薄くすることができ、さらに耐摩耗性に優れた摺動部材が得られる。
皮膜調整材のモース硬度が２以上であれば、皮膜調整材が軟らかすぎることがなく、皮膜調整材の皮膜を削る能力を確保できる傾向にある。また、皮膜調整材のモース硬度が６以下であれば、皮膜調整材が硬すぎることがないため皮膜調整材による摩耗量の増大を抑制することができる傾向にある。皮膜調整効果がより優れる皮膜調整材のモース硬度としては３〜５であることがより好ましく、４〜５であることが更に好ましい。
(Film conditioner)
The sliding material composition according to the present embodiment may contain (D) a film conditioner having a Mohs hardness of 2 to 6 (hereinafter sometimes referred to as a specific film conditioner). By adding the specific film adjusting material to the sliding material composition according to the present embodiment, the effect of scraping the film formed by the abrasion powder is expressed, the thickness of the film can be reduced, and the abrasion resistance is further improved. An excellent sliding member can be obtained.
If the Mohs hardness of the film conditioner is 2 or more, the film conditioner will not be too soft, and the ability of the film conditioner to scrape the film tends to be secured. Further, when the Mohs hardness of the coating film adjusting material is 6 or less, the coating film adjusting material will not be too hard, and there is a tendency that an increase in the amount of wear due to the coating film adjusting material can be suppressed. The Mohs hardness of the film adjusting material, which is more excellent in the film adjusting effect, is more preferably 3 to 5, and further preferably 4 to 5.
本実施形態に係る摺動材料組成物が（Ｄ）特定皮膜調整材を含有する場合、（Ｄ）特定皮膜調整材の含有量は、（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く摺動材料組成物１００質量部中に０．３質量部〜５質量部であることが好ましい。（Ｄ）特定皮膜調整材の含有量を、（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く摺動材料組成物１００質量部中に０．３質量部〜５質量部とすることで、摩耗粉により形成される皮膜を削る効果が発現しやすくなり、皮膜の厚みを薄くすることができ、さらに耐摩耗性に優れた摺動部材が得られる傾向にある。
また、（Ｄ）特定皮膜調整材の含有量が０．３質量部以上であれば、皮膜調整機能を発揮する傾向にある。一方、（Ｄ）特定皮膜調整材の含有量が５質量部以下であれば、皮膜調整材による研磨効果が大きくなりすぎることがなく、摩耗量が抑制される傾向にある。（Ｄ）特定皮膜調整材の含有量は、皮膜調整効果の観点から、０．５質量部〜３質量部であることがより好ましく、１質量部〜２質量部であることが更に好ましい。
When the sliding material composition according to the present embodiment contains (D) the specific film adjusting material, the content of the (D) specific film adjusting material is (C) the sliding material excluding the metal alkoxide compound and the metal chelate compound. It is preferably 0.3 to 5 parts by mass in 100 parts by mass of the composition. (D) The content of the specific film conditioner is set to 0.3 to 5 parts by mass in 100 parts by mass of the sliding material composition (C) excluding the metal alkoxide compound and the metal chelate compound, whereby the abrasion powder The effect of shaving the coating film formed by the above tends to be exhibited, the thickness of the coating film can be reduced, and a sliding member having excellent wear resistance tends to be obtained.
If the content of the (D) specific film adjusting material is 0.3 parts by mass or more, the film adjusting function tends to be exhibited. On the other hand, when the content of the (D) specific film adjusting agent is 5 parts by mass or less, the polishing effect of the film adjusting agent does not become too large, and the amount of wear tends to be suppressed. The content of the (D) specific film adjusting material is more preferably 0.5 parts by mass to 3 parts by mass, and further preferably 1 part by mass to 2 parts by mass, from the viewpoint of the film adjusting effect.
皮膜調整材としては、ケイ酸塩、アルミノケイ酸塩、炭酸塩、リン酸塩、ポリリン酸塩、メタリン酸塩、チタン酸塩、硫酸塩及び水酸化物からなる群より選択される少なくとも一種が挙げられる。
皮膜調整材としては、具体的には、長石、雲母、沸石（ゼオライト）、粘土鉱物、炭酸カルシウム、炭酸カリウム、炭酸バリウム、炭酸マグネシウム、炭酸リチウム、リン酸カルシウム、リン酸水素カルシウム、リン酸二水素カルシウム、二リン酸カルシウム（ピロリン酸カルシウム）、リン酸一マグネシウム、リン酸二マグネシウム、リン酸三マグネシウム、二リン酸マグネシウム（ピロリン酸マグネシウム）、メタリン酸マグネシウム、リン酸亜鉛、二リン酸亜鉛（ピロリン酸亜鉛）、チタン酸カリウム、チタン酸リチウムカリウム、チタン酸マグネシウム、チタン酸マグネシウムカリウム、チタン酸カルシウム、水酸化カルシウム、水酸化アルミニウム、水酸化亜鉛、硫酸カルシウム、硫酸マグネシウム、硫酸バリウム、硫酸亜鉛等が挙げられる。これらは１種を単独で用いても２種以上を組み合わせて用いてもよい。
Examples of the film modifier include at least one selected from the group consisting of silicate, aluminosilicate, carbonate, phosphate, polyphosphate, metaphosphate, titanate, sulfate and hydroxide. To be
Specific examples of the film conditioner include feldspar, mica, zeolite (zeolite), clay mineral, calcium carbonate, potassium carbonate, barium carbonate, magnesium carbonate, lithium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate. , Calcium diphosphate (calcium pyrophosphate), monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, magnesium diphosphate (magnesium pyrophosphate), magnesium metaphosphate, zinc phosphate, zinc diphosphate (zinc pyrophosphate) , Potassium titanate, lithium potassium titanate, magnesium titanate, magnesium potassium titanate, calcium titanate, calcium hydroxide, aluminum hydroxide, zinc hydroxide, calcium sulfate, magnesium sulfate, barium sulfate, zinc sulfate and the like. .. These may be used alone or in combination of two or more.
（固体潤滑剤）
本実施形態に係る摺動材料組成物は、固体潤滑剤を含有してもよい。本実施形態に係る摺動材料組成物が固体潤滑剤を含有することで、本実施形態の摺動部材の耐摩耗性が向上する。
本実施形態に係る摺動材料組成物が固体潤滑剤を含有する場合、固体潤滑剤の含有量は、（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く摺動材料組成物１００質量部中に１質量部〜１０質量部であることが好ましく、２質量部〜８質量部であることがより好ましく、３質量部〜７質量部であることが更に好ましい。固体潤滑剤の含有量が１０質量部以下であれば、摺動部材の強度の低下が抑制される傾向にある。
固体潤滑剤としては、タルク、二硫化モリブデン、二硫化タングステン、窒化ホウ素、フッ化黒鉛、ポリテトラフロロエチレン（ＰＴＦＥ）、メラミンシアヌレート（ＭＣＡ）等が挙げられる。
(Solid lubricant)
The sliding material composition according to the present embodiment may contain a solid lubricant. When the sliding material composition according to this embodiment contains a solid lubricant, the wear resistance of the sliding member of this embodiment is improved.
When the sliding material composition according to the present embodiment contains a solid lubricant, the content of the solid lubricant is 1 in 100 parts by mass of the sliding material composition excluding (C) the metal alkoxide compound and the metal chelate compound. The amount is preferably 10 parts by mass to 10 parts by mass, more preferably 2 parts by mass to 8 parts by mass, still more preferably 3 parts by mass to 7 parts by mass. When the content of the solid lubricant is 10 parts by mass or less, the reduction in strength of the sliding member tends to be suppressed.
Examples of the solid lubricant include talc, molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, polytetrafluoroethylene (PTFE), melamine cyanurate (MCA) and the like.
（離型剤）
本実施形態に係る摺動材料組成物は、離型剤を含有してもよい。
本実施形態に係る摺動材料組成物が離型剤を含有する場合、離型剤の含有量は、（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く摺動材料組成物１００質量部中に０．０５質量部〜５質量部であることが好ましく、０．５質量部〜３質量部であることがより好ましく、１質量部〜１．５質量部であることが更に好ましい。離型剤の含有量が５質量部以下であれば、摺動部材の強度、寸法安定性及び耐摩耗性の低下が抑制される傾向にある。
離型剤としては、流動パラフィン、パラフィンワックス、合成ポリエチレンワックス、ステアリン酸、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、メチレンビスステアリン酸アミド、エチレンビスステアリン酸アミド、ステアリン酸モノグリセリド、ステアリルステアレート、硬化油等が挙げられる。
(Release agent)
The sliding material composition according to the present embodiment may contain a release agent.
When the sliding material composition according to the present embodiment contains a releasing agent, the content of the releasing agent is 0 in 100 parts by mass of the sliding material composition excluding (C) the metal alkoxide compound and the metal chelate compound. It is preferably 0.05 part by mass to 5 parts by mass, more preferably 0.5 parts by mass to 3 parts by mass, and further preferably 1 part by mass to 1.5 parts by mass. When the content of the release agent is 5 parts by mass or less, the reduction in strength, dimensional stability and wear resistance of the sliding member tends to be suppressed.
Examples of the release agent include liquid paraffin, paraffin wax, synthetic polyethylene wax, stearic acid, zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, stearic acid amide, oleic acid amide, erucic acid amide, and methylenebisstearic acid. Examples thereof include amide, ethylenebisstearic acid amide, stearic acid monoglyceride, stearyl stearate, and hardened oil.
（かさ比重）
本実施形態の摺動部材のかさ比重は、１.６５ｇ／ｃｍ３〜１.８５ｇ／ｃｍ３であることが好ましい。本実施形態において、摺動部材のかさ比重は、ＪＩＳ Ｒ７２１２−１９９５に基づいて測定された値をいう。
摺動部材のかさ比重が１.６５ｇ／ｃｍ３以上であれば、十分な強度が得られる傾向にある。また、摺動部材としては比重が軽いほうが好まれることから、かさ比重は１.８５ｇ／ｃｍ３以下であることが好ましい。強度と比重の観点からは、１.７０ｇ／ｃｍ３〜１.８５ｇ／ｃｍ３であることが好ましく、１.７０ｇ／ｃｍ３〜１.８０ｇ／ｃｍ３であることがより好ましい。
摺動部材のかさ比重は摺動材料組成物の組成及び摺動部材の作製条件に依存して変化する。特に成形温度及び成形圧力に大きく依存することから、成形温度及び成形圧力を適宜調整し、かさ比重を調整することが好ましい。
(Bass specific gravity)
The bulk specific gravity of the sliding member of the present embodiment is preferably 1.65 g/cm 3 to 1.85 g/cm 3 . In the present embodiment, the bulk specific gravity of the sliding member refers to a value measured based on JIS R7212-1995.
When the bulk specific gravity of the sliding member is 1.65 g/cm 3 or more, sufficient strength tends to be obtained. Further, since it is preferred that the sliding member has a low specific gravity, the bulk specific gravity is preferably 1.85 g/cm 3 or less. From the intensity and the viewpoint of specific gravity is preferably 1.70g / cm 3 ~1.85g / cm 3 , more preferably 1.70g / cm 3 ~1.80g / cm 3 .
The bulk specific gravity of the sliding member changes depending on the composition of the sliding material composition and the manufacturing conditions of the sliding member. Particularly, since it largely depends on the molding temperature and the molding pressure, it is preferable to appropriately adjust the molding temperature and the molding pressure to adjust the bulk specific gravity.
本実施形態の摺動部材は寸法安定性に優れ、軸受け、シールリング、ローター、ブレード等に使用することができる。本実施形態は、特に、高温高湿で潤滑成分の存在しない環境下又は水中において優位性を発揮できる摺動部材を提供するものではあるが、通常の潤滑成分の存在しない環境下においても使用できる。本実施形態の摺動部材は、強度及び耐久性に優れるため、割れ及び破損が発生しにくく、軸受け、シールリング、ローター、ブレード等に好適に使用できる。 The sliding member of this embodiment has excellent dimensional stability and can be used for bearings, seal rings, rotors, blades, and the like. The present embodiment provides a sliding member that can exert its superiority particularly in an environment in which a lubricating component does not exist at high temperature and high humidity or in water, but can be used even in an environment in which a normal lubricating component does not exist. .. Since the sliding member of the present embodiment has excellent strength and durability, cracking and damage are unlikely to occur, and it can be suitably used for bearings, seal rings, rotors, blades and the like.
本実施形態の摺動部材の製造方法は特に限定されるものではない。例えば、本実施形態の摺動材料組成物を一般に使用されている方法で混錬し、成形して製造することができる。好ましくは、加熱加圧成形して製造される。詳細には、本実施形態に係る摺動材料組成物をレーディゲミキサー、ニーダー、アイリッヒミキサー等の混合機を用いて混合し、この混合物を成形金型にて予備成形し、得られた予備成形物を成形温度が１５０℃〜２５０℃、成形面圧が０．１ＭＰａ〜１０ＭＰａの条件で１分〜３０分の間成形し、得られた成形物を１８０℃〜３００℃で２時間〜１５時間熱処理することで得られる。 The method for manufacturing the sliding member of this embodiment is not particularly limited. For example, the sliding material composition of the present embodiment can be kneaded and molded by a commonly used method to be manufactured. Preferably, it is manufactured by hot pressing. Specifically, the sliding material composition according to the present embodiment was mixed using a mixer such as a Ledige mixer, a kneader, and an Erich mixer, and the mixture was preformed in a molding die to obtain the composition. The pre-molded product is molded at a molding temperature of 150° C. to 250° C. and a molding surface pressure of 0.1 MPa to 10 MPa for 1 minute to 30 minutes, and the obtained molded product is molded at 180° C. to 300° C. for 2 hours It is obtained by heat treatment for 15 hours.
以下、実施例により本発明を具体的に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described specifically with reference to Examples, but the scope of the present invention is not limited to these Examples.
〔実施例１〜８、比較例１〕
表１に実施例１〜８及び比較例１の組成及び特性を示す。
[Examples 1 to 8 and Comparative Example 1]
Table 1 shows the compositions and characteristics of Examples 1 to 8 and Comparative Example 1.
実施例及び比較例で用いられた材料は、以下の通りである。
Ａ−１：昭和電工株式会社製フェノール樹脂、ＢＲＰ−２４４４
Ｂ−１：株式会社シーケム製コークス、ＬＰＣＡ、平均粒径１８μｍ、Ｒ値１．１
Ｂ−２：オリエンタル産業株式会社製黒鉛、ＡＴ−Ｎｏ５、平均粒径３７μｍ、Ｒ値０．１
Ｄ−１：小野田化学工業株式会社製二リン酸カルシウム、モース硬度４
固体潤滑剤：セイコー産業株式会社製タルク、ＣＴＡ−１
離型剤：堺化学工業株式会社製ステアリン酸亜鉛、ＳＺ−Ｐ
Ｃ−１：オルガチックス ＴＣ−２０１（チタニウムジ−２−エチルヘキソキシビス（２−エチル−３−ヒドロキシヘキソキシド）［Ｔｉ（ＯＣ８Ｈ１７）２（Ｃ８Ｈ１７Ｏ２）２］）
Ｃ−２：オルガチックス ＴＣ−２２０（チタンオクチレングリコレート化合物）
Ｃ−３：オルガチックス ＴＡ−３０（チタンテトラ−２−エチルヘキソキシド［Ｔｉ（ＯＣ８Ｈ１７）４］）
Ｃ−４：オルガチックス ＴＣ−８００（チタンイソステアレート［Ｔｉ（Ｏ−ｉ−Ｃ３Ｈ７）（ＯＣＯＣ１７Ｈ３５）３］）
Ｃ−５：オルガチックス ＴＣ−１０４０（リン酸チタン化合物）
Ｃ−６：オルガチックス ＴＣ−１００（チタンジイソプロポキシビス（アセチルアセトネート）［Ｔｉ（Ｏ−ｉ−Ｃ３Ｈ７）２（Ｃ５Ｈ７Ｏ２）２］）
Ｃ−７：オルガチックス ＴＣ−４０１（チタンテトラアセチルアセトネート［Ｔｉ（Ｃ５Ｈ７Ｏ２）４］）
Ｃ−８：オルガチックス ＴＣ−７５０（チタンジイソプロポキシビス（エチルアセトアセテート）［Ｔｉ（Ｏ−ｉ−Ｃ３Ｈ７）２（Ｃ６Ｈ９Ｏ３）２］）
The materials used in the examples and comparative examples are as follows.
A-1: Showa Denko Phenol Resin, BRP-2444
B-1: Coke Co., Ltd. coke, LPCA, average particle size 18 μm, R value 1.1
B-2: Graphite manufactured by Oriental Sangyo Co., Ltd., AT-No5, average particle diameter 37 μm, R value 0.1
D-1: Onoda Chemical Co., Ltd. calcium diphosphate, Mohs hardness 4
Solid lubricant: Taiko, CTA-1 manufactured by Seiko Sangyo Co., Ltd.
Mold release agent: Sakai Chemical Industry Co., Ltd. zinc stearate, SZ-P
C-1: Orgatix TC-201 (titanium di-2-ethylhexoxide bis (2-ethyl-3-hydroxy-hexoxide) [Ti (OC 8 H 17 ) 2 (C 8 H 17 O 2) 2] )
C-2: Organix TC-220 (titanium octylene glycolate compound)
C-3: Orgatix TA-30 (titanium tetra-2-ethylhexoxide [Ti (OC 8 H 17) 4])
C-4: Orgatix TC-800 (titanium isostearate [Ti (O-i-C 3 H 7) (OCOC 17 H 35) 3])
C-5: Organix TC-1040 (titanium phosphate compound)
C-6: Orgatix TC-100 (titanium diisopropoxy bis (acetylacetonate) [Ti (O-i- C 3 H 7) 2 (C 5 H 7 O 2) 2])
C-7: Orgatix TC-401 (titanium tetra acetylacetonate [Ti (C 5 H 7 O 2) 4])
C-8: Orgatix TC-750 (titanium diisopropoxy bis (ethylacetoacetate) [Ti (O-i- C 3 H 7) 2 (C 6 H 9 O 3) 2])
表１の組成で配合した混合粉を双腕型ニーダー（株式会社栗本鐵工所製）に投入し、回転数２３ｍｉｎ−１、５０℃で１時間加熱混合した。得られた混合物を平均粒径２５μｍに粉砕し、粉砕物を１５０ｍｍ×２５０ｍｍ×５０ｍｍの金型にいれ、成形面圧０．２ＭＰａ、金型温度１８０℃、成形時間１０分で成形した。得られた成形体を２５０℃で１０時間熱処理したものを特性評価に用いた。 The mixed powder compounded with the composition shown in Table 1 was put into a double-arm kneader (manufactured by Kurimoto Steel Co., Ltd.), and heated and mixed at a rotation speed of 23 min −1 and 50° C. for 1 hour. The obtained mixture was pulverized to an average particle size of 25 μm, and the pulverized product was put into a mold of 150 mm×250 mm×50 mm and molded at a molding surface pressure of 0.2 MPa, a mold temperature of 180° C., and a molding time of 10 minutes. The obtained molded body was heat-treated at 250° C. for 10 hours and used for the characteristic evaluation.
（かさ比重測定）
かさ比重は、成形体から幅１０ｍｍ×厚み１０ｍｍ×長さ５０ｍｍの試験片を切り出し、ＪＩＳ Ｒ７２１２−１９９５に準じて測定した。
(Measurement of bulk specific gravity)
The bulk specific gravity was measured according to JIS R7212-1995 by cutting out a test piece having a width of 10 mm, a thickness of 10 mm, and a length of 50 mm from a molded body.
（曲げ強さ測定）
成形体から幅１０ｍｍ×厚み５ｍｍ×長さ８０ｍｍの試験片を切り出し測定に用いた。曲げ強さは、アムスラー式万能試験機（株式会社島津製作所製）を用い、試験片の厚み方向に荷重を加え、ＪＩＳ Ｋ６９１１−２００６に準じて測定した。
(Bending strength measurement)
A test piece having a width of 10 mm, a thickness of 5 mm and a length of 80 mm was cut out from the molded body and used for measurement. The bending strength was measured according to JIS K6911-2006 by applying a load in the thickness direction of the test piece using an Amsler universal testing machine (manufactured by Shimadzu Corporation).
（硬度測定）
硬度測定は、成形体から幅１０ｍｍ×厚み１０ｍｍ×長さ５０ｍｍの試験片を切り出し、Ｄ型ショア硬度計を用い、ＪＩＳ Ｚ２２４６−２０００に準じて測定した。
(Hardness measurement)
For the hardness measurement, a test piece having a width of 10 mm, a thickness of 10 mm and a length of 50 mm was cut out from the molded body, and the hardness was measured using a D-type Shore hardness meter according to JIS Z2246-2000.
（熱膨張係数測定）
成形体から幅５ｍｍ×厚み５ｍｍ×長さ１５ｍｍの試験片を切り出し、熱膨張係数の測定に供した。熱膨張係数は、熱膨張計ＤＬ−７０００ＲＨ（株式会社アルバック製）を用い、昇温速度を５℃／分とし、解析温度範囲を室温（２５℃）から１５０℃として線膨張係数を求めた。
(Measurement of thermal expansion coefficient)
A test piece having a width of 5 mm, a thickness of 5 mm, and a length of 15 mm was cut out from the molded body and subjected to measurement of the coefficient of thermal expansion. For the thermal expansion coefficient, a linear expansion coefficient was determined by using a thermal expansion meter DL-7000RH (manufactured by ULVAC, Inc.) with a temperature rising rate of 5° C./min and an analysis temperature range of room temperature (25° C.) to 150° C.
（摩耗試験）
チップオンディスク型摩耗試験機（株式会社エー・アンド・ディー製）を用い摺動摩耗試験を行った。成形体から幅１２ｍｍ×厚み８ｍｍ×長さ１８ｍｍに切り出した試験片を、ディスク（材質：ＳＵＳ３０４（ＪＩＳ Ｇ４３０３−２００５）、外径：８５ｍｍ、内径：１５ｍｍ）に押しあて、面圧：０．１ＭＰａ、周速：１０ｍ／ｓ、雰囲気温度１００℃の条件で８時間試験した。
摩耗量には１時間あたりの摩耗深さ（μｍ／時間）を用いた。摩擦係数には試験終了時の最終値を用いた。
(Abrasion test)
A sliding wear test was performed using a chip-on-disk type wear tester (manufactured by A&D Co., Ltd.). A test piece cut out from the molded body to a width of 12 mm, a thickness of 8 mm, and a length of 18 mm was pressed against a disc (material: SUS304 (JIS G4303-2005), outer diameter: 85 mm, inner diameter: 15 mm), and surface pressure: 0.1 MPa. The peripheral speed was 10 m/s and the ambient temperature was 100° C. for 8 hours.
The wear depth was the wear depth per hour (μm/hour). The final value at the end of the test was used as the friction coefficient.
（吸湿特性）
成形体から幅５ｍｍ×厚み２ｍｍ×長さ５０ｍｍに切り出した試験片を８５℃、８５％ＲＨに保持した恒温槽（楠本化成株式会社製、ＨＩＦＬＥＸ）に３３６時間放置し、吸湿処理した。重量変化率（％）は（（（処理後の質量）―（処理前の質量））／（処理前の質量））×１００で算出した。寸法変化率（％）は（（（処理後の幅の寸法）―（処理前の幅の寸法））／（処理前の幅の寸法））×１００で算出した。試験片の質量は分析用電子天秤（株式会社エー・アンド・デイ製）を用いて測定した。試験片の寸法はマイクロメーター（株式会社ミツトヨ製、ＭＤＥ−２５ＭＪ）で測定した。
(Hygroscopic property)
A test piece cut out from the molded body in a width of 5 mm, a thickness of 2 mm, and a length of 50 mm was left in a thermostatic chamber (HIFLEX, manufactured by Kusumoto Kasei Co., Ltd.) kept at 85° C. and 85% RH for 336 hours to absorb moisture. The weight change rate (%) was calculated by (((mass after treatment)-(mass before treatment))/(mass before treatment))×100. The dimensional change rate (%) was calculated by (((width dimension after treatment)−(width dimension before treatment))/(width dimension before treatment))×100. The mass of the test piece was measured using an analytical electronic balance (manufactured by A&D Co., Ltd.). The dimensions of the test piece were measured with a micrometer (MDE-25MJ manufactured by Mitutoyo Corporation).
実施例１〜８では（Ｃ）金属アルコキシド系化合物又は金属キレート化合物を添加することで、比較例１に比べて寸法変化率が小さくなっている。実施例１〜８に係る摺動部材では、機械特性、摩耗特性を著しく損なうことなく、寸法安定性に優れる摺動部材を提供しており、軸受け、シールリング、ブレード、ローター、プーリー等の摺動部材に使用できる。また、実施例１〜８に係る摺動部材は、高温高湿環境下又は水中において使用できる。 In Examples 1 to 8, by adding the (C) metal alkoxide compound or the metal chelate compound, the dimensional change rate was smaller than that in Comparative Example 1. The sliding members according to Examples 1 to 8 provide sliding members having excellent dimensional stability without significantly impairing mechanical characteristics and wear characteristics, and sliding elements such as bearings, seal rings, blades, rotors, and pulleys. It can be used as a moving member. Moreover, the sliding members according to Examples 1 to 8 can be used in a high temperature and high humidity environment or in water.
Claims (4)
前記（Ａ）フェノール樹脂の含有量が、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く前記摺動材料組成物１００質量部中に１５質量部〜３０質量部であり、
前記（Ｂ）炭素材料の含有量が、前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物を除く前記摺動材料組成物１００質量部中に６０質量部〜８５質量部であり、
前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種の合計の含有率が、前記（Ａ）フェノール樹脂に対して３質量％〜２０質量％であり、
前記（Ｃ）金属アルコキシド化合物及び金属キレート化合物からなる群より選択される少なくとも一種が、下記式（１）で表される化合物である摺動部材。
（式（１）中、Ｒ １ 、Ｒ ２ 、Ｒ ３ 及びＲ ４ は各々独立して、炭素の数が６〜１０の有機基を表す。） Formed by using a sliding material composition containing (A) a phenol resin, (B) a carbon material, and (C) at least one selected from the group consisting of a metal alkoxide compound and a metal chelate compound,
The content of the (A) phenolic resin is 15 parts by mass to 30 parts by mass in 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound,
The content of the (B) carbon material is 60 parts by mass to 85 parts by mass in 100 parts by mass of the sliding material composition excluding the (C) metal alkoxide compound and the metal chelate compound,
The metal alkoxide compound (C) and at least one total content of selected from the group consisting of metal chelate compounds, are three% to 20% by mass with respect to the (A) phenolic resin,
Wherein (C) at least one selected from the group consisting of metal alkoxide compounds and metal chelate compounds, compounds der Ru sliding member represented by the following formula (1).
(In the formula (1), R 1 , R 2 , R 3 and R 4 each independently represents an organic group having 6 to 10 carbon atoms.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016037715A JP6728769B2 (en) | 2016-02-29 | 2016-02-29 | Sliding member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016037715A JP6728769B2 (en) | 2016-02-29 | 2016-02-29 | Sliding member |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5531881B2 (en) * | 1971-09-22 | 1980-08-21 | ||
| JPS503442A (en) * | 1973-05-16 | 1975-01-14 | ||
| JPS5690120A (en) * | 1979-12-22 | 1981-07-22 | Taiho Kogyo Co Ltd | Sliding member |
| JPH0692547B2 (en) * | 1987-05-22 | 1994-11-16 | 松下電器産業株式会社 | Conductive paint |
| DE19749785A1 (en) * | 1997-11-11 | 1999-05-12 | Sgl Carbon Ag | Sliding body containing Zn phosphate |
| JP4358986B2 (en) * | 2000-12-20 | 2009-11-04 | リグナイト株式会社 | Method for producing carbon / phenolic resin molding material |
| JP2006193640A (en) * | 2005-01-14 | 2006-07-27 | Showa Highpolymer Co Ltd | Phenol resin composition and highly water-resistant cured phenol resin product using the same |
| JP5251341B2 (en) * | 2008-07-31 | 2013-07-31 | スターライト工業株式会社 | Heat-resistant sliding member |
| JP5696304B2 (en) * | 2010-06-25 | 2015-04-08 | パナソニックＩｐマネジメント株式会社 | Phenolic resin molding materials and phenolic resin moldings |
| JP6025434B2 (en) * | 2012-07-19 | 2016-11-16 | オイレス工業株式会社 | Sliding member |
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