JP2014012803A - Sliding resin member having excellent mold releasability and containing diamond fine particle having silicon and/or fluorine - Google Patents
Sliding resin member having excellent mold releasability and containing diamond fine particle having silicon and/or fluorine Download PDFInfo
- Publication number
- JP2014012803A JP2014012803A JP2012160947A JP2012160947A JP2014012803A JP 2014012803 A JP2014012803 A JP 2014012803A JP 2012160947 A JP2012160947 A JP 2012160947A JP 2012160947 A JP2012160947 A JP 2012160947A JP 2014012803 A JP2014012803 A JP 2014012803A
- Authority
- JP
- Japan
- Prior art keywords
- resin member
- fine particles
- diamond
- slidable
- diamond fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 105
- 239000010432 diamond Substances 0.000 title claims abstract description 105
- 239000010419 fine particle Substances 0.000 title claims abstract description 65
- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 43
- 239000011737 fluorine Substances 0.000 title claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 33
- 239000010703 silicon Substances 0.000 title claims abstract description 30
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 2
- 238000011282 treatment Methods 0.000 claims description 75
- 239000002113 nanodiamond Substances 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 32
- 230000005484 gravity Effects 0.000 claims description 23
- 238000004880 explosion Methods 0.000 claims description 19
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003682 fluorination reaction Methods 0.000 claims description 8
- 229910021647 smectite Inorganic materials 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 6
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002952 polymeric resin Substances 0.000 claims description 5
- 229920003002 synthetic resin Polymers 0.000 claims description 5
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 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
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000010455 vermiculite Substances 0.000 claims description 4
- 229910052902 vermiculite Inorganic materials 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 3
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 238000006884 silylation reaction Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract 1
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- 239000002904 solvent Substances 0.000 description 31
- 239000000843 powder Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229920000139 polyethylene terephthalate Polymers 0.000 description 20
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- 239000000203 mixture Substances 0.000 description 18
- 230000001590 oxidative effect Effects 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
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- 150000001875 compounds Chemical class 0.000 description 12
- -1 polybutylene terephthalate Polymers 0.000 description 12
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 8
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- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
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- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 229920006351 engineering plastic Polymers 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
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- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
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- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
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- 244000309464 bull Species 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 238000011109 contamination Methods 0.000 description 1
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- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- BHDAXLOEFWJKTL-UHFFFAOYSA-L dipotassium;carboxylatooxy carbonate Chemical compound [K+].[K+].[O-]C(=O)OOC([O-])=O BHDAXLOEFWJKTL-UHFFFAOYSA-L 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940013688 formic acid Drugs 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- LWFWUJCJKPUZLV-UHFFFAOYSA-N n-trimethylsilylacetamide Chemical compound CC(=O)N[Si](C)(C)C LWFWUJCJKPUZLV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- FGWRMMTYIZKYMA-UHFFFAOYSA-N tert-butyl-hydroxy-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)O FGWRMMTYIZKYMA-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 1
- LCNWHVJMIOOGTC-UHFFFAOYSA-N trimethylsilyl prop-2-ynoate Chemical compound C[Si](C)(C)OC(=O)C#C LCNWHVJMIOOGTC-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
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- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】耐擦傷性や耐摩耗性に優れるとともに、デジタル家電、家電製品、事務機器等の内部の送り機構、摺動機構に好適なオイルレス樹脂摺動部材を提供する。
【解決手段】基材中に、ケイ素を有するダイヤモンド微粒子及び／又はフッ素を有するダイヤモンド微粒子を含むことにより良好な摺動性を有することを特徴とする樹脂摺動部材。
【選択図】なしProvided is an oilless resin sliding member that is excellent in scratch resistance and wear resistance and that is suitable for an internal feed mechanism and sliding mechanism in digital home appliances, home appliances, office equipment and the like.
A resin sliding member characterized by having good sliding properties by including diamond fine particles having silicon and / or diamond fine particles having fluorine in a substrate.
[Selection figure] None
Description
本発明は、摺動性樹脂部材に関し、さらに詳しくは、耐擦傷性や耐摩耗性に優れるとともに、特に金型や押出し成型機等からの離型性に優れた摺動性樹脂部材、医療用、電気・電子部品製造用の用途に使用される摺動性樹脂部材に関するものである。 The present invention relates to a slidable resin member. More specifically, the slidable resin member has excellent scratch resistance and wear resistance, and particularly excellent releasability from a mold, an extrusion molding machine, and the like. The present invention relates to a slidable resin member used for applications for manufacturing electrical / electronic parts.
近年、市場が増大している携帯用の情報端末の入力装置として、成型加工された摺動性樹脂部材が多量に使用されている。 In recent years, a large amount of molded slidable resin members are used as input devices for portable information terminals whose market is increasing.
摺動性樹脂部材において、成形体の表面の平坦化が重要な課題である。特開平１１−３４８１８６号（特許文献１）には、樹脂構造物から成形される成形体の品質は、その表面の精度や品質にかかっており、すなわち摺動性樹脂部材の表面の精度や品質にかかっていると言っても過言ではない。さらに電気・電子部品製造で使用される摺動性樹脂部材は、その表面にフッ素樹脂やシリコーンを使用することで、離型性が良好で生産性が上がるが、転写による品質の不具合が発生するので、極力減らすことが検討されてきた。フッ素樹脂やシリコーン原材料中の低分子量オリゴマーや架橋反応時の未反応物が完全除去できず、僅かな転写が起こる。成型部品に転写したフッ素樹脂やシリコーンはその後の製造工程において、コンタミネーションや密着性を阻害し、品質や耐久性の不具合をもたらしている。 In the slidable resin member, flattening the surface of the molded body is an important issue. In JP-A-11-348186 (Patent Document 1), the quality of a molded body molded from a resin structure depends on the accuracy and quality of the surface, that is, the accuracy and quality of the surface of the slidable resin member. It is not an exaggeration to say that it depends on. Furthermore, slidable resin members used in the manufacture of electrical and electronic parts use fluororesin and silicone on the surface, so that the mold release is good and the productivity is increased, but quality defects due to transfer occur. Therefore, it has been studied to reduce as much as possible. Low molecular weight oligomers in fluororesins and silicone raw materials and unreacted substances during the crosslinking reaction cannot be completely removed, resulting in slight transfer. The fluororesin or silicone transferred to the molded parts hinders contamination and adhesion in subsequent manufacturing processes, resulting in defects in quality and durability.
一方、特開２００４−４２６５３号（特許文献２）には、雲母、合成雲母、シリカ、アルミナ、酸化カルシウム、チタニア、酸化ジルコニウム、酸化亜鉛、フッ化マグネシウム、スメクタイト、合成スメクタイト、バーミキュライト、ＩＴＯ（酸化インジウム／酸化錫）、ＡＴＯ（酸化アンチモン／酸化錫）、酸化錫、酸化インジウム、酸化カドミウム及び酸化アンチモン等の無機微粒子を添加する技術が開示されている。特許文献２は、これらの無機微粒子を添加することによりブロッキングを防止できると記載している。 On the other hand, JP-A-2004-42653 (Patent Document 2) discloses mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (oxidation). A technique of adding inorganic fine particles such as indium / tin oxide, ATO (antimony oxide / tin oxide), tin oxide, indium oxide, cadmium oxide, and antimony oxide is disclosed. Patent Document 2 describes that blocking can be prevented by adding these inorganic fine particles.
しかしながら、特許文献２に記載の無機微粒子は、離型性が不十分で、より離型性の良好な、耐擦傷性、耐摩耗性に優れた滑り性良好なフィラーの開発が望まれている。 However, the inorganic fine particles described in Patent Document 2 have insufficient releasability, and it is desired to develop a filler with better releasability, better scratch resistance and higher wear resistance, and better sliding properties. .
一方摺動性樹脂部材にシリコーン系化合物やフッ素系化合物を含有させ、樹脂構造物表面に離型性を付与することが行われている。しかしながら、これらのシリコーン系化合物やフッ素系化合物はその表面から徐々に失われて効果が長期にわたって持続しないという欠点がある。 On the other hand, a slidable resin member is allowed to contain a silicone compound or a fluorine compound to impart releasability to the surface of the resin structure. However, these silicone compounds and fluorine compounds have the disadvantage that they are gradually lost from the surface and the effect does not last for a long time.
長期間の離型性能を保持しながら、フッ素樹脂やシリコーンの転写を防いで、品質の不具合を抑え、耐擦傷性、耐摩耗性に優れた摺動性樹脂部材の出現が望まれていた。 There has been a demand for the appearance of a slidable resin member that prevents transfer of fluororesin and silicone while maintaining long-term release performance, suppresses defects in quality, and has excellent scratch resistance and wear resistance.
従って、本発明の目的は、耐擦傷性や耐摩耗性に優れるとともに、離型性に優れた樹脂構造物を提供することである。 Accordingly, an object of the present invention is to provide a resin structure that is excellent in scratch resistance and wear resistance and also excellent in mold release properties.
上記目的に鑑み鋭意研究の結果、本発明者らは、樹脂構造物に、ダイヤモンド微粒子をケイ素化処理及び／又はフッ素化処理してなるケイ素及び／又はフッ素を有するダイヤモンド微粒子を樹脂構造物に含有させることにより、ケイ素やフッ素樹脂がナノダイヤモンドに固定化されているため、転写による品質の不具合の発生が長期間なく、耐擦傷性、耐摩耗性が飛躍的に改良し、摺動性樹脂部材となることを見出し、本発明に想到した。 As a result of diligent research in view of the above object, the present inventors have included in the resin structure diamond fine particles containing silicon and / or fluorine obtained by siliconizing and / or fluorinating diamond fine particles in the resin structure. Since silicon and fluororesin are fixed to nanodiamond, there is no generation of quality defects due to transfer, and scratch resistance and wear resistance are dramatically improved. As a result, the present invention has been conceived.
すなわち、本発明の摺動性樹脂部材は、ケイ素を有するダイヤモンド微粒子及び／又はフッ素を有するダイヤモンド微粒子を含む摺動性樹脂部材で形成されたことを特徴とする。 That is, the slidable resin member of the present invention is characterized in that it is formed of a slidable resin member containing diamond fine particles having silicon and / or diamond fine particles having fluorine.
本発明の摺動性樹脂部材は、ケイ素及びフッ素を有するダイヤモンド微粒子を含む摺動性樹脂部材で形成されたことを特徴とする。 The slidable resin member of the present invention is formed of a slidable resin member containing diamond fine particles containing silicon and fluorine.
前記ケイ素を有するダイヤモンド微粒子はケイ素化処理されたダイヤモンド微粒子であり、前記フッ素を有するダイヤモンド微粒子はフッ素化処理されたダイヤモンド微粒子であるのが好ましい。 Preferably, the silicon-containing diamond fine particles are siliconized diamond fine particles, and the fluorine-containing diamond fine particles are fluorinated diamond fine particles.
前記ケイ素及びフッ素を有するダイヤモンド微粒子は、ケイ素化処理及びフッ素化処理されたダイヤモンド微粒子であるのが好ましい。 The diamond fine particles having silicon and fluorine are preferably diamond fine particles that have been siliconized and fluorinated.
前記ケイ素化処理はシリル化処理であるのが好ましく、前記フッ素化処理はフルオロアルキル基含有オリゴマーによる処理であるのが好ましい。 The siliconization treatment is preferably silylation treatment, and the fluorination treatment is preferably treatment with a fluoroalkyl group-containing oligomer.
前記ダイヤモンド微粒子は特に限定されないが、天然ダイヤモンド、合成ダイヤモンドいずれでもよいが、爆射法で得られたナノダイヤモンドであるのが好ましい。 The diamond fine particles are not particularly limited, and may be either natural diamond or synthetic diamond, but are preferably nanodiamonds obtained by an explosion method.
前記摺動性樹脂部材は、さらに無機微粒子を含むのが好ましい。 The slidable resin member preferably further contains inorganic fine particles.
前記無機微粒子は、雲母、合成雲母、シリカ、アルミナ、酸化カルシウム、チタニア、酸化ジルコニウム、酸化亜鉛、フッ化マグネシウム、スメクタイト、合成スメクタイト、バーミキュライト、ＩＴＯ（酸化インジウム／酸化錫）、ＡＴＯ（酸化アンチモン／酸化錫）、酸化錫、酸化インジウム、酸化カドミウム及び酸化アンチモンからなる群から選ばれた少なくとも１種であるのが好ましい。 The inorganic fine particles include mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO (antimony oxide / It is preferably at least one selected from the group consisting of (tin oxide), tin oxide, indium oxide, cadmium oxide and antimony oxide.
無機微粒子の平均粒子径は、１０〜３００ｎｍが好ましく、１０〜２００ｎｍがより好ましく、３０〜１５０ｎｍが最も好ましい。平均粒子径が、１０ｎｍ以上の場合は、より小さい表面粗さを有する摺動性樹脂部材を形成することができ、一方、前記平均粒子径が３００ｎｍ以下の場合は、より優れた光学特性を有する摺動性樹脂部材を形成できる。 The average particle size of the inorganic fine particles is preferably 10 to 300 nm, more preferably 10 to 200 nm, and most preferably 30 to 150 nm. When the average particle size is 10 nm or more, a slidable resin member having a smaller surface roughness can be formed. On the other hand, when the average particle size is 300 nm or less, the optical properties are more excellent. A slidable resin member can be formed.
鱗片状及び／又は不規則薄片状の無機微粒子を使用することにより、より優れた摺動性樹脂部材が形成できる。このような形状を有する無機微粒子としては、シリカ、チタニア、酸化ジルコニウム、ＩＴＯ等を鱗片状に成形したもの、雲母、合成雲母、スメクタイト、合成スメクタイト、バーミキュライト等が挙げられる。 By using scale-like and / or irregular flaky inorganic fine particles, a more excellent slidable resin member can be formed. Examples of the inorganic fine particles having such a shape include silica, titania, zirconium oxide, ITO and the like formed into a scale, mica, synthetic mica, smectite, synthetic smectite, vermiculite and the like.
摺動性樹脂部材中の無機微粒子の含有量は、０．０１〜６重量％であるのか好ましく、０．０１〜５．５重量％であるのがより好ましい。前記含有量が、０．０１重量％以上であると、より優れた離型性を有する樹脂構造物を形成することができ、６重量％以下であると、より優れた光学特性を有する摺動性樹脂部材を形成できる。 The content of the inorganic fine particles in the slidable resin member is preferably 0.01 to 6% by weight, and more preferably 0.01 to 5.5% by weight. When the content is 0.01% by weight or more, a resin structure having more excellent releasability can be formed, and when the content is 6% by weight or less, sliding having more excellent optical characteristics can be achieved. A functional resin member can be formed.
前記摺動性樹脂部材はエンジニアリングプラスティック（エンプラ）として使用され、その形状等は用途に応じて適宜変わるので特に限定されない。 The slidable resin member is used as an engineering plastic (engineering plastic), and the shape and the like thereof are not particularly limited because they change as appropriate according to the application.
エンプラの多くは、家電製品内部の▲１▼平歯車▲２▼ピニオン▲３▼はすば歯車や▲４▼転がり軸受け、▲５▼すべり軸受け▲６▼磁気軸受け▲７▼流体軸受けといった機構部品に多用されている。▲４▼転がり軸受けに、玉軸受け（ボール軸受け、ボールベアリング）▲５▼すべり軸受けに、ころ軸受（円筒コロ、円錐コロ、自動調心コロ、ローラーベアリングｅｔｃ．）があり、これらは油がなくとも耐摩耗性に優れ、軽量で錆びず、複雑な形状も精度良く成形加工でき大量生産に向く。
その他、無給軸受け、静圧軸受け、含油軸受け、流体動圧軸受けなどがある。また、家電に限らず電気製品全般の筐体にも、広く採用されている。十分な強度を持ち、内部／外部の複雑な形状を容易に作り得るため装置の小型化が可能で、塗装が不要であったり、塗装時も定着が良いものが選べ、携帯機器などに最適となっている。Many engineering plastics are mechanical parts such as (1) spur gear (2) pinion (3) helical gear, (4) rolling bearing, (5) sliding bearing, (6) magnetic bearing, and (7) fluid bearing inside home appliances. Is often used. (4) Rolling bearings have ball bearings (ball bearings, ball bearings) (5) Sliding bearings have roller bearings (cylindrical rollers, conical rollers, self-aligning rollers, roller bearings etc.), which are oil-free. Both have excellent wear resistance, are lightweight and do not rust, and can be formed and processed with high accuracy even for complex shapes, making them suitable for mass production.
In addition, there are non-bearing bearings, hydrostatic bearings, oil-impregnated bearings, fluid dynamic bearings, and the like. In addition, it is widely adopted not only for home appliances but also for housings for electrical products in general. Since it has sufficient strength and can easily create complicated shapes inside and outside, it is possible to reduce the size of the equipment, and it is possible to select one that does not require painting or that has good fixation even during painting. It has become.
前記摺動性樹脂部材の基材は特に限定されないが、ポリアセタール（ＰＯＭ）、ポリアミド（ＰＡ）、ポリカーボネート（ＰＣ）、変性ポリフェニレンエーテル（ｍ−ＰＰＥ）、ポリブチレンテレフタレート（ＰＢＴ）や、ガラスファイバー強化ポリエチレンテレフタレート（ＧＦ−ＰＥＴ）、高分子量ポリエチレン（ＵＨＰＥ）、シンジオタクチックポリスチレン（ＳＰＳ）等のエンジニアリング・プラスチックが挙げられる。 Although the base material of the slidable resin member is not particularly limited, polyacetal (POM), polyamide (PA), polycarbonate (PC), modified polyphenylene ether (m-PPE), polybutylene terephthalate (PBT), and glass fiber reinforced Engineering plastics such as polyethylene terephthalate (GF-PET), high molecular weight polyethylene (UHPE), and syndiotactic polystyrene (SPS) can be mentioned.
更に、非晶ポリアリレート（ＰＡＲ）、ポリスルホン（ＰＳＦ）ポリエーテルサルフォン（ＰＥＳ）、ポリフェニレンスルファイド（ＰＰＳ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリイミド（ＰＩ）、ポリエーテルイミド（ＰＥＩ）、フッ素樹脂、液晶ポリマー（ＬＣＰ）等のスーパーエンジニアリング・プラスチックが挙げられる。 Furthermore, amorphous polyarylate (PAR), polysulfone (PSF) polyethersulfone (PES), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polyimide (PI), polyetherimide (PEI), fluorine Examples include super engineering plastics such as resins and liquid crystal polymers (LCP).
上記以外、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート等のポリエステル系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリエチレン、ポリプロピレン、ポリメチルペンテン、脂環式構造含有重合体等のポリオレフィン系ポリマー等の構造物、繊維、フイルム、セロファン、ジアセチルセルロース、トリアセチルセルロース、アセチルセルロースブチレート等のフイルムの他、ポリ塩化ビニルフイルム、ポリ塩化ビニリデンフイルム、ポリビニルアルコールフイルム、エチレン−酢酸ビニル共重合体フイルム、ポリスチレンフイルム、ポリスルホンフイルム、ポリエーテルエーテルケトンフイルム、ポリエーテルスルホンフイルム、ポリエーテルイミドフイルム、ポリイミドフイルム、フッ素樹脂フイルム、ポリアミドフイルム等に用いることができる。 Other than the above, polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, acrylic polymers such as polymethyl methacrylate, polyolefin polymers such as polyethylene, polypropylene, polymethylpentene, alicyclic structure-containing polymers Structures such as fiber, film, cellophane, diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, etc., polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film Polystyrene film, Polysulfone film, Polyetheretherketone film, Polyethersulfone film, Polyetherimide film Beam, can be used for the polyimide film, a fluororesin film, a polyamide film or the like.
本発明の摺動性樹脂部材は、耐擦傷性、耐摩耗性に優れ、かつ離型性が良いのでデジタル家電、家電製品、事務機器等の内部の送り機構、摺動機構に使用の歯車、軸受け、ボールベアリング、カム機構、コロ、送り機構等の生産および使用に好適である。特に滑り性が良いので、カム、シリンダー、ボールベアリングのオイルレス樹脂摺動部材として好適である。 The slidable resin member of the present invention has excellent scratch resistance, abrasion resistance, and good releasability, so that it can be used in digital home appliances, home appliances, office equipment and other internal feed mechanisms, sliding gears, It is suitable for production and use of bearings, ball bearings, cam mechanisms, rollers, feed mechanisms and the like. Particularly, since it has good sliding properties, it is suitable as an oilless resin sliding member for cams, cylinders and ball bearings.
摺動性樹脂部材中のケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、及びケイ素及びフッ素を有するダイヤモンド微粒子の含有量は、特に限定されないが、摺動性樹脂部材に対して、合計で０．００１〜３０質量％であるのが好ましく、０．０１〜１０質量％であるのがより好ましく、０．１〜５質量％が最も好ましい。添加量が０．００１質量％未満であると耐擦傷性や耐摩耗性に劣り、特に離形層の剥離特性が安定しなくなり３０質量％を超えると凝集が起こりやすく粗大凝集物が発生して好ましくない。ケイ素を有するダイヤモンド微粒子及びフッ素を有するダイヤモンド微粒子を混合して使用する場合は、それらの比率はどのような比率でも良いが、２：８〜９：１の範囲であるのが好ましく、３：７〜８：２の範囲であるのがより好ましい。 The content of silicon-containing diamond fine particles, fluorine-containing diamond fine particles, and silicon and fluorine-containing diamond fine particles in the slidable resin member is not particularly limited. The content is preferably 001 to 30% by mass, more preferably 0.01 to 10% by mass, and most preferably 0.1 to 5% by mass. If the amount added is less than 0.001% by mass, the scratch resistance and wear resistance are poor, and the release characteristics of the release layer become unstable, and if it exceeds 30% by mass, agglomeration tends to occur and coarse aggregates are generated. It is not preferable. When diamond fine particles having silicon and diamond fine particles having fluorine are mixed and used, the ratio thereof may be any ratio, but is preferably in the range of 2: 8 to 9: 1. More preferably, it is in the range of ˜8: 2.
摺動性樹脂部材には、さらに必要に応じて、アニオン、カチオン性やノニオン性界面活性剤、光安定剤や紫外線吸収剤、触媒、重合禁止剤、レベリング剤、増粘剤、沈殿防止剤、難燃剤、有機・無機顔料・染料の各種添加剤、添加助剤等を含むことができる。 The sliding resin member further includes an anion, a cationic or nonionic surfactant, a light stabilizer or an ultraviolet absorber, a catalyst, a polymerization inhibitor, a leveling agent, a thickener, a suspending agent, if necessary. It can contain flame retardants, various additives of organic / inorganic pigments / dyes, additive aids, and the like.
本発明のケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子は、２〜５００ｎｍ程度のダイヤモンド微粒子を、ケイ素原子を含有する基及び／又はフッ素原子を含有する基で修飾したものである。すなわち、ケイ素のみを有するダイヤモンド微粒子であってもよいし、フッ素のみを有するダイヤモンド微粒子であってもよいし、ケイ素及びフッ素を有するダイヤモンド微粒子であってもよい。 The silicon-containing diamond fine particles, the fluorine-containing diamond fine particles, and the silicon and fluorine-containing diamond fine particles of the present invention have a silicon fine particle diameter of about 2 to 500 nm with a group containing a silicon atom and / or a group containing a fluorine atom. It is a modified one. That is, diamond fine particles having only silicon, diamond fine particles having only fluorine, or diamond fine particles having silicon and fluorine may be used.
ケイ素原子を含有する基及び／又はフッ素原子を含有する基を修飾するためのダイヤモンド微粒子としては、天然ダイヤモンド、合成ダイヤモンドいずれでも良いが、爆射法で得られたナノダイヤモンドを用いるのが好ましい。爆射法で得られた未精製のナノダイヤモンドは、ナノダイヤモンドの表面をグラファイト系炭素が覆ったコア／シェル構造を有しており黒く着色している。未精製のナノダイヤモンドをこのまま用いても良いが、より着色の少ない摺動性樹脂部材を得るためには、未精製のナノダイヤモンドを酸化処理し、グラファイト相の一部又はほぼ全部を除去して用いるのが好ましい。 The diamond fine particles for modifying the group containing a silicon atom and / or the group containing a fluorine atom may be either natural diamond or synthetic diamond, but it is preferable to use nanodiamond obtained by an explosion method. The unpurified nanodiamond obtained by the explosion method has a core / shell structure in which the surface of the nanodiamond is covered with graphite-based carbon and is colored black. Unpurified nanodiamonds may be used as they are, but in order to obtain a slidable resin member with less coloring, the unpurified nanodiamonds are oxidized to remove part or almost all of the graphite phase. It is preferable to use it.
未精製のナノダイヤモンドは、グラファイトリッチで、２〜１０ｎｍ程度のダイヤモンドの一次粒子からからなるが、凝集したナノダイヤモンドのメジアン径は０．５μｍ〜数μｍ（動的光散乱法）の二次粒子である。又、酸化処理して得られたナノダイヤモンドは、２〜１０ｎｍ程度のダイヤモンドの一次粒子からなるメジアン径３０〜２５０ｎｍ（動的光散乱法）の二次粒子である。グラファイト相を除去することにより、着色成分はほとんどなくなるが、微量に残ったグラファイト系炭素の表面に−ＣＯＯＨ、−ＯＨ等の親水性官能基が存在するため、水、アルコール、グリコール等の親水的な溶剤への分散に優れている。 Unrefined nanodiamond is composed of graphite-rich primary diamond particles of about 2 to 10 nm. Aggregated nanodiamonds have a median diameter of 0.5 μm to several μm (dynamic light scattering method). It is. Nanodiamonds obtained by oxidation treatment are secondary particles having a median diameter of 30 to 250 nm (dynamic light scattering method) composed of diamond primary particles of about 2 to 10 nm. By removing the graphite phase, there is almost no coloring component, but there are hydrophilic functional groups such as -COOH and -OH on the surface of the remaining graphite-based carbon. Excellent dispersion in various solvents.
ケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子は、前記爆射法で得られた未精製のナノダイヤモンド、又は前記酸化処理して得られたナノダイヤモンドを、ケイ素化処理及び／又はフッ素化処理することによって得られ、前記ナノダイヤモンド表面に存在する−ＣＯＯＨ、−ＯＨ等の親水性官能基にケイ素原子を有する基、及び／又はフッ素原子を有する基が結合したものである。 Diamond fine particles having silicon, diamond fine particles having fluorine, and diamond fine particles having silicon and fluorine are obtained by converting unpurified nanodiamonds obtained by the above-mentioned explosion method or nanodiamonds obtained by the above oxidation treatment into silicon. A group having a silicon atom and / or a group having a fluorine atom is bonded to a hydrophilic functional group such as —COOH and —OH obtained on the surface of the nanodiamond, which is obtained by fluorination treatment and / or fluorination treatment. Is.
ケイ素を有するダイヤモンド微粒子、又はケイ素及びフッ素を有するダイヤモンド微粒子中のケイ素原子の量は、特に限定されないが、ダイヤモンド微粒子に対して、０．１〜２５質量％であるのが好ましく、０．２〜２０質量％であるのがより好ましい。フッ素を有するダイヤモンド微粒子、又はケイ素及びフッ素を有するダイヤモンド微粒子中のフッ素原子の量は特に限定されないが、ダイヤモンド微粒子に対して、０．１〜２０質量％であるのが好ましく、０．２〜１５質量％であるのがより好ましい。 The amount of silicon atoms in the diamond fine particles having silicon or the diamond fine particles having silicon and fluorine is not particularly limited, but is preferably 0.1 to 25% by mass with respect to the diamond fine particles, and 0.2 to It is more preferably 20% by mass. The amount of fluorine atoms in the diamond fine particles having fluorine or the diamond fine particles having silicon and fluorine is not particularly limited, but is preferably 0.1 to 20% by mass with respect to the diamond fine particles, and preferably 0.2 to 15%. More preferably, it is mass%.
ケイ素を有するダイヤモンド微粒子、フッ素を有するダイヤモンド微粒子、並びにケイ素及びフッ素を有するダイヤモンド微粒子は、ダイヤモンド微粒子をケイ素化処理及び／又はフッ素化処理することにより得ることができる。ケイ素化処理は、フッ素化処理よりも先に行うのが好ましい。 Diamond fine particles having silicon, diamond fine particles having fluorine, and diamond fine particles having silicon and fluorine can be obtained by siliconizing and / or fluorinating diamond fine particles. The siliconization treatment is preferably performed prior to the fluorination treatment.
（１）ダイヤモンド微粒子の製造方法
ダイヤモンド微粒子としては、爆射法により得られた未精製のナノダイヤモンド（ＢＤと言うこともある。）、又はそれを酸化処理しグラファイト系炭素の一部又は全部を除去したナノダイヤモンドが好ましい。前記酸化処理して得られるナノダイヤモンドとしては、後述のグラファイト相の一部が除去されたナノダイヤモンド（グラファイト−ダイヤモンド粒子と呼ぶ）及びグラファイト相がほとんど除去された精製ナノダイヤモンド粒子が好ましい。(1) Method for producing diamond fine particles As diamond fine particles, unpurified nanodiamond (also referred to as BD) obtained by an explosion method, or a part or all of graphite-based carbon by oxidizing it. The removed nanodiamond is preferred. The nanodiamond obtained by the oxidation treatment is preferably nanodiamond from which a part of the graphite phase described later is removed (referred to as graphite-diamond particles) and purified nanodiamond particles from which the graphite phase is almost removed.
酸化処理したナノダイヤモンドの比重は、グラファイト系炭素（グラファイトの比重：２．２５ｇ／ｃｍ３）の残存量が少なくなればなるほどダイヤモンドの比重（３．５０ｇ／ｃｍ３）に近づく。
従って、精製度が高くグラファイト系炭素の残存量が少ないほど比重が高くなる。本発明で用いるナノダイヤモンドの比重は２．５５ｇ／ｃｍ３（ダイヤモンド２４体積％）以上３．５０ｇ／ｃｍ３（ダイヤモンド１００体積％）であるのが好ましい。３．０ｇ／ｃｍ３（ダイヤモンド８４体積％）以上３．４６ｇ／ｃｍ３（ダイヤモンド９７体積％）以下であるのがより好ましく、３．３８ｇ／ｃｍ３（ダイヤモンド９０体積％）以上であるのが最も好ましい。本発明では天然ダイヤモンドも含むので、上限の比重は３．５０ｇ／ｃｍ３である。なおナノダイヤモンド中のダイヤモンドの体積％は、前記ダイヤモンドの比重３．５０ｇ／ｃｍ３及びグラファイトの比重２．２５ｇ／ｃｍ３を用いて、ナノダイヤモンドの比重から算出した。The specific gravity of the nano-diamonds oxidation treatment, graphitic carbon (graphite density: 2.25g / cm 3) closer to the remaining amount is small, the more an diamond density (3.50g / cm 3).
Therefore, the specific gravity increases as the degree of purification increases and the remaining amount of graphite carbon decreases. The specific gravity of the nanodiamond used in the present invention is preferably 2.55 g / cm 3 (diamond 24% by volume) or more and 3.50 g / cm 3 (diamond 100% by volume). It is more preferably 3.0 g / cm 3 (diamond 84% by volume) or more and 3.46 g / cm 3 (diamond 97% by volume) or more, and 3.38 g / cm 3 (diamond 90% by volume) or more. Most preferred. Since natural diamond is also included in the present invention, the upper limit specific gravity is 3.50 g / cm 3 . The volume percentage of diamond in the nanodiamond was calculated from the specific gravity of the nanodiamond using the specific gravity of the diamond of 3.50 g / cm 3 and the specific gravity of graphite of 2.25 g / cm 3 .
（２）粒子の比重測定法
本発明で用いるナノダイヤモンドの真比重は以下の操作により測定できる。
１．試料を比重ビンに入れ、蓋をした状態で秤量し重量を求める。
２．蒸留水を試料の少し上位まで入れ、煮沸法で気泡を完全に除去する。
３．２５℃蒸留水を入れ、恒温槽（２５℃）に１０分間入れて、基線まで満たす。
４．恒温槽から比重ビンを取り出し、外側の水分を良く拭き取った後秤量し重量を測る。
５．比重ビンをよく洗浄し、２５℃の蒸留水のみを入れ、恒温槽（２５℃）に１０分間入れて、基線まで満たし、４と同様に重量を測定する。
６．上記操作で得た値から以下の式（１）により真比重ρを求める。
ρ＝［（Ｗ−Ｐ）・ｄｗ］／［（Ｗ１−Ｐ）−（Ｗ２−Ｐ）］ ・・・（１）
（ここで、Ｗ：比重ビン＋試料の重量、
Ｗ１：比重ビンに蒸留水のみを満たしたときの重量、
Ｗ２：比重ビンに試料と蒸留水を満たし、完全に気泡を満たした（空気を除いた）時の重量、
Ｐ：比重ビンの重量、及び
ｄｗ：測定時の温度における水の比重である。）(2) Particle Specific Gravity Measurement Method The true specific gravity of the nanodiamond used in the present invention can be measured by the following operation.
1. Place the sample in a specific gravity bottle and weigh it with the lid on to determine the weight.
2. Add distilled water to the top of the sample and remove bubbles completely by boiling.
3. Add distilled water at 25 ° C., put in a thermostatic bath (25 ° C.) for 10 minutes, and fill to the baseline.
4). Take out the specific gravity bottle from the thermostatic bath, wipe off the moisture on the outside well, weigh and weigh.
5. Thoroughly wash the specific gravity bottle, put only distilled water at 25 ° C., put it in a constant temperature bath (25 ° C.) for 10 minutes, fill up to the baseline, and measure the weight in the same way as 4.
6). From the value obtained by the above operation, the true specific gravity ρ is obtained by the following equation (1).
ρ = [(W−P) · dw] / [(W1−P) − (W2−P)] (1)
(W: specific gravity bin + sample weight,
W1: Weight when specific gravity bottle is filled only with distilled water,
W2: Weight when the specific gravity bottle is filled with the sample and distilled water and completely filled with air bubbles (excluding air),
P: weight of specific gravity bottle, and dw: specific gravity of water at the temperature at the time of measurement. )
未精製の粗ダイヤモンドの酸化処理方法としては、（ａ）硝酸等の共存下で高温高圧処理する方法（酸化処理Ａ）、（ｂ）水及び／又はアルコールからなる超臨界流体中で処理する方法（酸化処理Ｂ）、（ｃ）水及び／又はアルコールからなる溶媒に酸素を共存させて、前記溶媒の標準沸点以上の温度及び０．１ＭＰａ（ゲージ圧）以上の圧力で処理する方法（酸化処理Ｃ）、又は（ｄ）３８０〜４５０℃で酸素を含む気体により処理する方法（酸化処理Ｄ）が挙げられる。これらの酸化処理は、単独で行ってもよいし、組合せて行っても良い。酸化処理を組合せる場合は、爆射法で得られた未精製の粗ダイヤモンドにまず酸化処理Ａを施し、さらに酸化処理Ｂ〜Ｃのいずれかを施すのが好ましい。 As an oxidation treatment method for unpurified crude diamond, (a) a method of high-temperature and high-pressure treatment in the presence of nitric acid or the like (oxidation treatment A), and (b) a method of treatment in a supercritical fluid comprising water and / or alcohol. (Oxidation treatment B), (c) A method in which oxygen is allowed to coexist in a solvent comprising water and / or alcohol, and the treatment is performed at a temperature higher than the normal boiling point of the solvent and at a pressure higher than 0.1 MPa (gauge pressure) C) or (d) A method of treating with a gas containing oxygen at 380 to 450 ° C. (oxidation treatment D). These oxidation treatments may be performed alone or in combination. When combining the oxidation treatment, it is preferable to first subject the unpurified crude diamond obtained by the explosion method to oxidation treatment A, and then to any one of oxidation treatments B to C.
爆射法で得られた未精製の粗ダイヤモンドに酸化処理Ａを施すことによりグラファイト相の一部が除去されたナノダイヤモンド（グラファイト−ダイヤモンド粒子）が得られ、このグラファイト−ダイヤモンド粒子に酸化処理Ｂ〜Ｃのいずれかの処理を施すことにより前記グラファイト相をさらに除去することができる。 By subjecting unpurified crude diamond obtained by the explosion method to oxidation treatment A, nanodiamond (graphite-diamond particles) from which a part of the graphite phase has been removed is obtained, and this graphite-diamond particles are subjected to oxidation treatment B. The graphite phase can be further removed by performing any one of the processes of ~ C.
（１）爆射法によるＢＤの合成
爆射法によるＢＤの合成は、例えば、水と多量の氷を満たした純チタン製の耐圧容器に、電気雷管を装着した爆薬［例えば、ＴＮＴ（トリニトロトルエン）／ＨＭＸ（シクロテトラメチレンテトラニトラミン）＝５０／５０］を胴内に収納させ、片面プラグ付き鋼鉄製パイプを水平に沈め、この鋼鉄製パイプに鋼鉄製のヘルメット状カバーを被覆して、前記爆薬を爆裂させることにより行うことができる。反応生成物としてのＢＤは容器中の水中から回収する。(1) Synthesis of BD by explosion method Synthesis of BD by explosion method is, for example, an explosive in which an electric detonator is mounted on a pressure vessel made of pure titanium filled with water and a large amount of ice [for example, TNT (trinitrotoluene ) / HMX (cyclotetramethylenetetranitramine) = 50/50], and a steel pipe with a single-sided plug is submerged horizontally, and this steel pipe is covered with a steel helmet-like cover, This can be done by exploding the explosive. BD as a reaction product is recovered from the water in the container.
前記爆射法は、Ｓｃｉｅｎｃｅ，Ｖｏｌ．１３３，Ｎｏ．３４６７（１９６１），ｐｐ１８２１−１８２２、特開平１−２３４３１１号、特開平２−１４１４１４号、Ｂｕｌｌ．Ｓｏｃ．Ｃｈｅｍ．Ｆｒ．Ｖｏｌ．１３４（１９９７），ｐｐ．８７５−８９０、Ｄｉａｍｏｎｄ ａｎｄ Ｒｅｌａｔｅｄ ｍａｔｅｒｉａｌｓ Ｖｏｌ．９（２０００），ｐｐ８６１−８６５、Ｃｈｅｍｉｃａｌ Ｐｈｙｓｉｃｓ Ｌｅｔｔｅｒｓ，２２２（１９９４），ｐｐ．３４３−３４６、Ｃａｒｂｏｎ，Ｖｏｌ．３３，Ｎｏ．１２（１９９５），ｐｐ．１６６３−１６７１、Ｐｈｙｓｉｃｓ ｏｆ ｔｈｅ Ｓｏｌｉｄ Ｓｔａｔｅ，Ｖｏｌ．４２，Ｎｏ．８（２０００），ｐｐ．１５７５−１５７８、Ｋ．Ｘｕ．Ｚ．Ｊｉｎ，Ｆ．Ｗｅｉ ａｎｄ Ｔ．Ｊｉａｎｇ，Ｅｎｅｒｇｅｔｉｃ Ｍａｔｅｒｉａｌｓ，１，１９（１９９３）、特開昭６３−３０３８０６号、特開昭５６−２６７１１報、英国特許第１１５４６３３号、特開平３−２７１１０９号、特表平６−５０５６９４号（ＷＯ９３／１３０１６号）、炭素，第２２巻，Ｎｏ．２，１８９〜１９１頁（１９８４）、Ｖａｎ Ｔｈｉｅｉ．Ｍ．＆Ｒｅｃ．，Ｆ．Ｈ．，Ｊ．Ａｐｐｌ．Ｐｈｙｓ．６２，ｐｐ．１７６１〜１７６７（１９８７）、特表平７−５０５８３１号（ＷＯ９４／１８１２３号）、米国特許第５８６１３４９号及び特開２００６−２３９５１１号等に記載の方法を用いることができる。 The explosion method is described in Science, Vol. 133, no. 3467 (1961), pp 1821-1822, JP-A-1-234411, JP-A-2-141414, Bull. Soc. Chem. Fr. Vol. 134 (1997), pp. 875-890, Diamond and Related materials Vol. 9 (2000), pp 861-865, Chemical Physics Letters, 222 (1994), pp. 343-346, Carbon, Vol. 33, no. 12 (1995), pp. 1663-1671, Physics of the Solid State, Vol. 42, no. 8 (2000), pp. 1575-1578, K.M. Xu. Z. Jin, F.J. Wei and T.W. Jiang, Energy Materials, 1, 19 (1993), JP-A-63-303806, JP-A-56-26711, British Patent No. 1156633, JP-A-3-271109, JP-A-6-505694 (WO93). No. 13016), Carbon, Vol. 2, 189-191 (1984), Van Thiei. M.M. & Rec. , F.A. H. , J .; Appl. Phys. 62, pp. 1761 to 1767 (1987), JP 7-505831 (WO94 / 18123), US Pat. No. 5,861,349, JP-A-2006-239511, and the like can be used.
（２）酸化処理工程
（ｉ）酸化処理Ａ
爆射法で得られた未精製の粗ダイヤモンド（ＢＤ）は、まず酸化処理Ａを施すのが好ましい。
酸化処理Ａを施すことによりグラファイト相の一部が除去されたグラファイト−ダイヤモンド粒子が得られる。酸化処理Ａは、（ａ）爆射法で得られたＢＤを、酸中で酸化性分解処理する工程、（ｂ）酸化性分解処理したＢＤを、さらに厳しい条件で処理する酸化性エッチング処理工程、（ｃ）酸化性エッチング処理後の液を中和する工程、（ｄ）脱溶媒工程、及び（ｅ）洗浄工程からなり、必要に応じてグラファイト−ダイヤモンド粒子分散液の（ｆ）ｐＨ及び濃度を調製する工程、又は（ｇ）乾燥して微粉末とする工程からなる。(2) Oxidation treatment step (i) Oxidation treatment A
The unpurified crude diamond (BD) obtained by the explosion method is preferably first subjected to oxidation treatment A.
By performing the oxidation treatment A, graphite-diamond particles from which a part of the graphite phase has been removed are obtained. The oxidation treatment A includes (a) a step of oxidizing decomposition of BD obtained by the explosion method in acid, and (b) an oxidizing etching treatment step of processing BD subjected to oxidation decomposition treatment under more severe conditions. (C) a step of neutralizing the solution after the oxidative etching treatment, (d) a desolvation step, and (e) a washing step, and (f) pH and concentration of the graphite-diamond particle dispersion as necessary. Or (g) a step of drying into a fine powder.
（ａ）酸化性分解処理工程
回収したＢＤを５５〜５６質量％の濃硝酸、又は濃硝酸と濃硫酸との混合物とともに、１．４ＭＰａ程度の圧力及び１５０〜１８０℃程度の温度で１０〜３０分間処理し、電気雷管等の混入金属、炭素等の夾雑物等の不純物を分解する。(A) Oxidative decomposition treatment step The recovered BD is 10 to 30 at a pressure of about 1.4 MPa and a temperature of about 150 to 180 ° C. together with 55 to 56 mass% concentrated nitric acid or a mixture of concentrated nitric acid and concentrated sulfuric acid. Dissolve impurities such as contaminated metals such as electric detonator and carbon, and impurities such as carbon.
（ｂ）酸化性エッチング処理工程
酸化性分解処理したＢＤは、濃硝酸中で酸化性分解処理よりもさらに厳しい条件（例えば、１．４Ｍｐａ、２００〜２４０℃）で行う。このような条件で１０〜３０分処理すると、ＢＤ表面を被覆する硬質炭素、すなわちグラファイトを大部分除去することができる。(B) Oxidative Etching Process Step The BD subjected to the oxidative decomposition process is performed in concentrated nitric acid under conditions more severe than the oxidative decomposition process (for example, 1.4 Mpa, 200 to 240 ° C.). When treated for 10 to 30 minutes under such conditions, most of the hard carbon covering the BD surface, that is, graphite, can be removed.
（ｃ）中和工程
酸化性エッチング処理後のグラファイト−ダイヤモンド粒子を含む硝酸水溶液（ｐＨが２〜６．９５）に、それ自身又はその分解反応生成物が揮発性の塩基性物質を加えて中和反応させる。塩基性物質の添加によりｐＨ７．０５〜１２に上昇する。前記塩基性物質を使用することにより、凝集したグラファイト−ダイヤモンド粒子内に浸透した塩基が、粒子内の硝酸と反応し、ガス化することにより凝集体を個々のグラファイト−ダイヤモンド粒子に解体するといった効果が得られる。この工程により、グラファイト−ダイヤモンド粒子の大きな比表面積及び孔部吸着空間が形成されるものと思われる。(C) Neutralization step The aqueous solution of nitric acid (pH 2 to 6.95) containing graphite-diamond particles after oxidative etching is added with a volatile basic substance itself or its decomposition reaction product. Let the sum react. The pH rises to 7.05-12 by the addition of basic substances. By using the basic substance, the base that has penetrated into the agglomerated graphite-diamond particles reacts with nitric acid in the particles, and gasifies to break up the agglomerates into individual graphite-diamond particles. Is obtained. This process seems to form a large specific surface area and pore adsorption space of the graphite-diamond particles.
塩基性材料としては、アンモニア、ヒドラジン、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エタノールアミン、プロピルアミン、イソプロピルアミン、ジプロピルアミン、アリルアミン、アニリン、Ｎ，Ｎ−ジメチルアニリン、ジイソプロピルアミン、ジエチレントリアミンやテトラエチレンペンタミンのようなポリアルキレンポリアミン、２−エチルヘキシルアミン、シクロヘキシルアミン、ピペリジン、ホルムアミド、Ｎ，Ｎ−メチルホルムアミド、尿素等を挙げることができる。 Basic materials include ammonia, hydrazine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, propylamine, isopropylamine, dipropylamine, allylamine, aniline, N, N-dimethylaniline, diisopropylamine. And polyalkylene polyamines such as diethylenetriamine and tetraethylenepentamine, 2-ethylhexylamine, cyclohexylamine, piperidine, formamide, N, N-methylformamide, urea and the like.
（ｄ）脱溶媒工程
得られたグラファイト−ダイヤモンド粒子を含む液は、遠心分離、デカンテーション等により脱溶媒するのが好ましい。(D) Solvent removal process It is preferable to remove the solvent containing the obtained graphite-diamond particles by centrifugation, decantation, or the like.
（ｅ）水洗工程
脱溶媒したグラファイト−ダイヤモンド粒子はデカンテーション法により水洗するのが好ましい。洗浄操作は３回以上行うのが好ましい。水洗したグラファイト−ダイヤモンド粒子は、再度遠心分離し、脱水するのが好ましい。(E) Water washing step It is preferable that the desolvated graphite-diamond particles are washed with water by a decantation method. The washing operation is preferably performed three times or more. The graphite-diamond particles washed with water are preferably centrifuged again and dehydrated.
（ｆ）ｐＨ及び濃度を調製する工程
グラファイト−ダイヤモンド粒子分散液は、ｐＨ４〜１０、好ましくはｐＨ５〜８、より好ましくはｐＨ６〜７．５に調節する。グラファイト−ダイヤモンド粒子濃度は０．０５〜１６％、好ましくは０．１〜１２％、より好ましくは１〜５％に調製するのが好ましい。(F) Step of adjusting pH and concentration The graphite-diamond particle dispersion is adjusted to pH 4 to 10, preferably pH 5 to 8, more preferably pH 6 to 7.5. The graphite-diamond particle concentration is preferably adjusted to 0.05 to 16%, preferably 0.1 to 12%, more preferably 1 to 5%.
グラファイト相を有するナノダイヤモンド（グラファイト−ダイヤモンド粒子）はさらに酸化処理Ｂ〜Ｄを施すことによりグラファイト層をさらに除去するのが好ましい。もちろんＢＤに直接酸化処理Ｂ〜Ｄを施しても良い。 It is preferable that the nanodiamond (graphite-diamond particles) having a graphite phase is further subjected to oxidation treatments B to D to further remove the graphite layer. Of course, the oxidation treatments B to D may be directly performed on the BD.
（ｉｉ）酸化処理Ｂ
酸化処理Ｂは、（ａ）グラファイト相を有するナノダイヤモンドと、酸化性化合物と、水及び／又はアルコールからなる溶媒とからなる混合物Ａ（単に「混合物Ａ」とよぶことがある）を調製し、（ｂ）この混合物Ａを、溶媒の臨界点以上の温度及び圧力にした状態でグラファイト相を有するナノダイヤモンドを処理し、（ｃ）得られた精製ダイヤモンド粒子を含む液を遠心分離して溶媒を除去する工程を有する。さらに、脱溶媒した精製ダイヤモンド粒子を（ｄ）水洗及び遠心分離により脱水する工程を設けるのが好ましい。工程（ｃ）と（ｄ）の間に、必要に応じて、脱溶媒した精製ダイヤモンド粒子を（ｅ）塩基性溶液で中和する工程、及び（ｆ）弱酸で処理する工程を設けてもよい。工程（ｃ）又は（ｄ）で得られた精製ダイヤモンド粒子は乾燥して微粉末にする。(Ii) Oxidation treatment B
Oxidation treatment B prepares a mixture A (sometimes referred to simply as “mixture A”) consisting of (a) nanodiamond having a graphite phase, an oxidizing compound, and a solvent comprising water and / or alcohol; (B) The nano-diamond having the graphite phase is treated with the mixture A at a temperature and pressure higher than the critical point of the solvent, and (c) the liquid containing the obtained purified diamond particles is centrifuged to remove the solvent. Removing. Furthermore, it is preferable to provide (d) a step of dewatering the purified diamond particles that have been desolvated by water washing and centrifugation. Between steps (c) and (d), if necessary, a step of neutralizing the desolvated purified diamond particles with (e) a basic solution and a step of (f) treating with a weak acid may be provided. . The refined diamond particles obtained in step (c) or (d) are dried to a fine powder.
（ａ）混合物Ａの調製工程
混合物Ａは、グラファイト相を有するナノダイヤモンドの粉末に、酸化性化合物、及び水及び／又はアルコールからなる溶媒を混合することにより調製する。又は、前記溶媒にあらかじめグラファイト相を有するナノダイヤモンドを分散した液に、前記酸化性化合物又はその溶液を添加して調製しても良い。混合物Ａには、酸化性化合物による酸化反応を促進させるため、塩基性化合物又は酸化性化合物を添加しても良い。(A) Preparation Step of Mixture A Mixture A is prepared by mixing nanodiamond powder having a graphite phase with an oxidizing compound and a solvent composed of water and / or alcohol. Alternatively, the oxidizing compound or a solution thereof may be added to a liquid in which nanodiamond having a graphite phase is dispersed in advance in the solvent. In order to promote the oxidation reaction by the oxidizing compound, a basic compound or an oxidizing compound may be added to the mixture A.
酸化性化合物としては、硝酸、過酸化水素、過炭酸ナトリウム、過炭酸カリウム、過ホウ酸ナトリウム、過ホウ酸カリウム、次亜塩素酸ナトリウム、次亜塩素酸カリウム、亜塩素酸ナトリウム、亜塩素酸カリウム、塩素酸リチウム、塩素酸ナトリウム、塩素酸カリウム、過塩素酸リチウム、過塩素酸ナトリウム、過塩素酸カリウム、過マンガン酸ナトリウム、過マンガン酸カリウム、マンガン酸ナトリウム、マンガン酸カリウム、過硫酸ナトリウム、過硫酸カリウム、重クロム酸カリウム、クロム酸カリウム等が挙げられ、硝酸及び過酸化水素が好ましい。特に酸化性化合物を単独で使用する場合は、過酸化水素を使用するのが最も好ましい。 Examples of oxidizing compounds include nitric acid, hydrogen peroxide, sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, sodium hypochlorite, potassium hypochlorite, sodium chlorite, chlorite Potassium, lithium chlorate, sodium chlorate, potassium chlorate, lithium perchlorate, sodium perchlorate, potassium perchlorate, sodium permanganate, potassium permanganate, sodium manganate, potassium manganate, sodium persulfate Potassium persulfate, potassium dichromate, potassium chromate and the like, and nitric acid and hydrogen peroxide are preferred. In particular, when an oxidizing compound is used alone, it is most preferable to use hydrogen peroxide.
酸性化合物としては、硝酸、硫酸、塩酸、リン酸、ホウ酸、フッ酸、臭化水素酸等の無機酸、及び蟻酸、酢酸、メタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸等の有機酸が挙げられ、無機酸が好ましく、硝酸がより好ましい。 Examples of acidic compounds include inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, boric acid, hydrofluoric acid, and hydrobromic acid, and organic acids such as formic acid, acetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. An acid is mentioned, An inorganic acid is preferable and nitric acid is more preferable.
塩基性化合物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、四ホウ酸リチウム、四ホウ酸ナトリウム、四ホウ酸カリウム、アンモニア等が挙げられる。 Basic compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, lithium tetraborate, sodium tetraborate, potassium tetraborate , Ammonia and the like.
酸化性化合物と酸性化合物とを組合せて使用する場合は、過酸化水素と硝酸との組合せが好ましく、酸化性化合物と塩基性化合物とを組合せて使用する場合は、過酸化水素とアンモニアとの組合せが好ましい。 A combination of hydrogen peroxide and nitric acid is preferable when using a combination of an oxidizing compound and an acidic compound, and a combination of hydrogen peroxide and ammonia is used when a combination of an oxidizing compound and a basic compound is used. Is preferred.
溶媒としては、水、アルコール又はこれらの混合液を用いる。アルコールとしては炭素数１〜３の低級アルコールが好ましい。低級アルコールの具体例として、メタノール、エタノール、ｎ−プロパノール、イソプロパノール及びこれらの混合液が挙げられる。 As the solvent, water, alcohol or a mixture thereof is used. The alcohol is preferably a lower alcohol having 1 to 3 carbon atoms. Specific examples of the lower alcohol include methanol, ethanol, n-propanol, isopropanol, and a mixture thereof.
（ｂ）超臨界処理工程
混合物Ａを溶媒の臨界点以上の温度及び圧力で処理する。処理温度は溶媒の臨界温度以上、６００℃以下であるのが好ましく、５５０℃以下であるのがより好ましい。処理圧力は溶媒の臨界圧力以上、１００ＭＰａ以下であるのが好ましく、７０ＭＰａ以下であるのがより好ましく、５０ＭＰａ以下であるのが最も好ましい。処理時間は温度及び圧力により適宜設定すればよいが、１〜２４時間が好ましい。(B) Supercritical treatment step Mixture A is treated at a temperature and pressure above the critical point of the solvent. The treatment temperature is preferably not lower than the critical temperature of the solvent and not higher than 600 ° C., more preferably not higher than 550 ° C. The treatment pressure is preferably not less than the critical pressure of the solvent and not more than 100 MPa, more preferably not more than 70 MPa, and most preferably not more than 50 MPa. The treatment time may be appropriately set depending on the temperature and pressure, but is preferably 1 to 24 hours.
（ｃ）脱溶媒工程
酸化処理Ａと同様にして行う。(C) Desolvation step Performed in the same manner as oxidation treatment A.
（ｄ）水洗工程
酸化処理Ａと同様にして行う。(D) Washing step Performed in the same manner as oxidation treatment A.
（ｅ）中和工程
工程（ｃ）で脱溶媒した精製ダイヤモンド粒子を、水酸化ナトリウム、水酸化カリウム等の塩基で中和してもよい。塩基性溶液の濃度は０．０１〜０．５ｍｏｌ／Ｌが好ましい。脱溶媒した精製ダイヤモンド粒子に塩基性溶液を添加し、超音波処理するのが好ましい。(E) Neutralization process The refined diamond particles desolvated in the process (c) may be neutralized with a base such as sodium hydroxide or potassium hydroxide. The concentration of the basic solution is preferably 0.01 to 0.5 mol / L. It is preferable to add a basic solution to the purified diamond particles from which the solvent has been removed, followed by sonication.
（ｆ）弱酸処理工程
工程（ｅ）で中和した精製ダイヤモンド粒子を弱酸溶液で洗浄するのが好ましい。弱酸溶液の例として、０．０１〜０．５ｍｏｌ／Ｌの塩酸が挙げられる。中和した精製ダイヤモンド粒子に弱酸溶液を添加し、超音波処理するのが好ましい。(F) Weak acid treatment step The purified diamond particles neutralized in step (e) are preferably washed with a weak acid solution. An example of a weak acid solution is 0.01 to 0.5 mol / L hydrochloric acid. It is preferable to add a weak acid solution to the neutralized purified diamond particles and sonicate.
（ｉｉｉ）酸化処理Ｃ
酸化処理Ｃは、（ａ）グラファイト相を有するナノダイヤモンドと、水及び／又はアルコールからなる溶媒とからなる混合物Ｂを調製し、（ｂ）この混合物Ｂに酸素を共存させた状態で、処理溶媒の標準沸点以上の温度及び０．１ＭＰａ（ゲージ圧）以上の圧力でグラファイト相を有するナノダイヤモンドを処理し、（ｃ）得られた精製ダイヤモンド粒子を含む液を遠心分離して溶媒を除去する工程を有する。さらに、脱処理溶媒した精製ダイヤモンド粒子を（ｄ）水洗及び遠心分離により脱水する工程を設けるのが好ましい。工程（ｃ）又は（ｄ）で得られた精製ダイヤモンド粒子は乾燥して微粉末にする。(Iii) Oxidation treatment C
In the oxidation treatment C, a mixture B composed of (a) nanodiamond having a graphite phase and a solvent composed of water and / or alcohol is prepared, and (b) a treatment solvent in a state where oxygen is present in the mixture B. A process of treating nanodiamond having a graphite phase at a temperature equal to or higher than a normal boiling point and a pressure equal to or higher than 0.1 MPa (gauge pressure), and (c) removing the solvent by centrifuging the liquid containing the obtained purified diamond particles. Have Further, it is preferable to provide a step (d) of dewatering the purified diamond particles that have been subjected to the detreatment solvent by washing with water and centrifuging. The refined diamond particles obtained in step (c) or (d) are dried to a fine powder.
（ａ）混合物Ｂの調製工程
混合物Ｂは、グラファイト相を有するナノダイヤモンドと、水及び／又はアルコールからなる溶媒とを混合することにより調製する。混合物Ｂ中のグラファイト相を有するナノダイヤモンドの濃度は、０．０５〜１６質量％が好ましく、０．１〜１０質量％がより好ましく、０．５〜５質量％が最も好ましい。この濃度が１６質量％を超えると、精製が不十分となる恐れがある。一方０．０５質量％未満であると、回収時のロスの割合が多くなり生産性が悪化する。(A) Preparation process of mixture B Mixture B is prepared by mixing nanodiamond having a graphite phase and a solvent composed of water and / or alcohol. The concentration of nanodiamond having a graphite phase in the mixture B is preferably 0.05 to 16% by mass, more preferably 0.1 to 10% by mass, and most preferably 0.5 to 5% by mass. If this concentration exceeds 16% by mass, purification may be insufficient. On the other hand, if it is less than 0.05% by mass, the ratio of loss at the time of recovery increases and productivity deteriorates.
溶媒としては、前記混合物Ａの調製で用いることのできるものと同じものが使用できる。 As the solvent, the same solvents that can be used in the preparation of the mixture A can be used.
（ｂ）精製処理工程
混合物Ｂをオートクレーブに入れ、酸素を導入する。酸素の導入量は、グラファイト相を有するナノダイヤモンド中のグラファイト１ｇに対して、０．１モル以上が好ましく、０．１５モル以上がより好ましく、０．２モル以上が最も好ましい。この導入量の上限は特に制限されない。(B) Purification treatment step The mixture B is put into an autoclave and oxygen is introduced. The amount of oxygen introduced is preferably 0.1 mol or more, more preferably 0.15 mol or more, and most preferably 0.2 mol or more with respect to 1 g of graphite in the nanodiamond having a graphite phase. The upper limit of the introduction amount is not particularly limited.
処理溶媒の標準沸点Ｔｂ以上及び０．１ＭＰａ（ゲージ圧）以上となるように、オートクレーブ内の温度及び圧力を調整する。処理溶媒のＴｂ以上及び０．１ＭＰａ（ゲージ圧）以上にする限り、処理溶媒を亜臨界状態［Ｔｂ以上の温度及び０．１ＭＰａ（ゲージ圧）以上の圧力で、かつ臨界温度Ｔｃ未満及び／又は臨界圧力Ｐｃ未満の状態］にしてもよいし、超臨界状態にしてもよい。亜臨界又は超臨界状態の酸素及び処理溶媒により、グラファイト相を効率的に選択酸化することができる。 The temperature and pressure in the autoclave are adjusted so that the processing solvent has a normal boiling point Tb or higher and 0.1 MPa (gauge pressure) or higher. As long as the processing solvent is at least Tb and at least 0.1 MPa (gauge pressure), the processing solvent is in a subcritical state [temperature above Tb and pressure above 0.1 MPa (gauge pressure) and below the critical temperature Tc and / or It may be in a state less than the critical pressure Pc] or may be in a supercritical state. The graphite phase can be efficiently selectively oxidized by subcritical or supercritical oxygen and the processing solvent.
処理温度の下限は（処理溶媒の臨界温度Ｔｃ−１５０℃）が好ましく、（Ｔｃ−１００℃）がより好ましい。処理温度の上限は８００℃が好ましく、６００℃がより好ましい。処理圧力の下限は、処理溶媒の臨界圧力Ｐｃの３０％が好ましく、Ｐｃの５０％がより好ましく、Ｐｃの７０％が最も好ましい。処理圧力の上限は７０ＭＰａが好ましく、５０ＭＰａがより好ましい。処理時間は温度及び圧力により適宜設定すればよいが、０．１〜２４時間が好ましい。 The lower limit of the treatment temperature is preferably (critical temperature of the treatment solvent Tc-150 ° C), more preferably (Tc-100 ° C). The upper limit of the treatment temperature is preferably 800 ° C, more preferably 600 ° C. The lower limit of the processing pressure is preferably 30% of the critical pressure Pc of the processing solvent, more preferably 50% of Pc, and most preferably 70% of Pc. The upper limit of the treatment pressure is preferably 70 MPa, more preferably 50 MPa. The treatment time may be appropriately set depending on the temperature and pressure, but is preferably 0.1 to 24 hours.
（ｃ）脱溶媒工程
酸化処理Ａと同様にして行う。(C) Desolvation step Performed in the same manner as oxidation treatment A.
（ｄ）水洗工程
酸化処理Ａと同様にして行う。(D) Washing step Performed in the same manner as oxidation treatment A.
（ｉｖ）酸化処理Ｄ
酸化処理Ｄは、前記グラファイト相を有するナノダイヤモンドを反応管に入れ、常圧下で酸素を含む気体を流しながら３７５〜６３０℃に加熱する工程を有する。加熱温度は３８０〜４５０℃であるのが好ましく、４００〜４３０℃が最も好ましい。酸素を含む気体は、酸素ガス、空気等を使用できるが、簡便さから空気が好ましい。(Iv) Oxidation treatment D
The oxidation treatment D includes a step of putting nanodiamond having the graphite phase into a reaction tube and heating to 375 to 630 ° C. while flowing a gas containing oxygen under normal pressure. The heating temperature is preferably 380 to 450 ° C, and most preferably 400 to 430 ° C. As the gas containing oxygen, oxygen gas, air, or the like can be used, but air is preferable for simplicity.
（３）メディア分散処理
酸化処理を効率よく行い、着色の少ない精製ダイヤモンド粒子を得るために、酸化処理Ｂ〜Ｄの前にＢＤ又はグラファイト−ダイヤモンド粒子をビーズミル等の公知のメディア分散法により粉砕するのが好ましい。ビーズミルによる分散は、ジルコニアビーズを使用するのが好ましい。ＢＤ又はグラファイト−ダイヤモンド粒子をメディア分散することにより、メジアン径を１００ｎｍ以下にするのが好ましく、５０ｎｍ以下にするのがより好ましく、３０ｎｍ以下にするのが最も好ましい。(3) Media dispersion treatment BD or graphite-diamond particles are pulverized by a known media dispersion method such as a bead mill before the oxidation treatments B to D in order to efficiently carry out oxidation treatment and obtain purified diamond particles with little coloring. Is preferred. For dispersion by a bead mill, zirconia beads are preferably used. By media dispersion of BD or graphite-diamond particles, the median diameter is preferably 100 nm or less, more preferably 50 nm or less, and most preferably 30 nm or less.
［２］ケイ素化処理
前記爆射法で得られた未精製のナノダイヤモンド、又は前記酸化処理して得られたナノダイヤモンドに、シリル化剤、アルコキシシラン、シランカップリング剤等を反応させることによりナノダイヤモンドの表面にある水酸基等の親水性基を、ケイ素を含む有機基に置換することができる。ケイ素化処理は、シリル化剤を用いるのが好ましい。[2] Siliconation treatment By reacting unpurified nanodiamond obtained by the above-mentioned explosion method or nanodiamond obtained by the above oxidation treatment with a silylating agent, alkoxysilane, silane coupling agent, or the like. A hydrophilic group such as a hydroxyl group on the surface of the nanodiamond can be substituted with an organic group containing silicon. In the siliconization treatment, a silylating agent is preferably used.
好ましいシリル化剤としては、トリエチルクロロシラン、トリメチルクロロシラン、ジエチルジクロロシラン、ジメチルジクロロシラン、アセトキシトリメチルシラン、アセトキシシラン、ジアセトキシジメチルシラン、メチルトリアセトキシシラン、フェニルトリアセトキシシラン、ジフェニルジアセトキシシラン、トリメチルエトキシシラン、トリメチルメトキシシラン、２−トリメチルシロキシペント−２−エン−４−オン、ｎ−（トリメチルシリル）アセトアミド、２−（トリメチルシリル）酢酸、ｎ−（トリメチルシリル）イミダゾール、トリメチルシリルプロピオレート、ノナメチルトリシラザン、ヘキサメチルジシラザン、ヘキサメチルジシロキサン、トリメチルシラノール、トリエチルシラノール、トリフェニルシラノール、ｔ−ブチルジメチルシラノール、ジフェニルシランジオール等が挙げられる。本発明に用いられるシリル化剤は、これらの化合物に限定されない。 Preferred silylating agents include triethylchlorosilane, trimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, acetoxytrimethylsilane, acetoxysilane, diacetoxydimethylsilane, methyltriacetoxysilane, phenyltriacetoxysilane, diphenyldiacetoxysilane, trimethylethoxy Silane, trimethylmethoxysilane, 2-trimethylsiloxypent-2-en-4-one, n- (trimethylsilyl) acetamide, 2- (trimethylsilyl) acetic acid, n- (trimethylsilyl) imidazole, trimethylsilylpropiolate, nonamethyltrisilazane , Hexamethyldisilazane, hexamethyldisiloxane, trimethylsilanol, triethylsilanol, triphenylsilanol t- butyldimethylsilanol include diphenylsilane diol and the like. The silylating agent used in the present invention is not limited to these compounds.
シリル化剤溶液の溶媒はヘキサン、シクロヘキサン、ペンタン、ヘプタン等の炭化水素類、アセトン、メチルイソプチルケトン等のケトン類、ベンゼン、トルエン等の芳香族化合物が好ましい。 The solvent of the silylating agent solution is preferably a hydrocarbon such as hexane, cyclohexane, pentane or heptane, a ketone such as acetone or methylisobutyl ketone, or an aromatic compound such as benzene or toluene.
シリル化剤の種類や濃度にもよるが、シリル化反応は１０〜４０℃で十分攪拌しながら進行させるのが好ましい。１０℃未満では反応が進行しにくく、４０℃超ではナノダイヤモンド表面に均一にシリル化されなくなる。例えば、トリエチルクロロシランのヘキサン溶液をシリル化剤として使用した場合、１０〜４０℃で１０〜４０時間程度攪拌しながら反応させると、ナノダイヤモンド表面の水酸基が十分にシリル修飾される。 Although depending on the type and concentration of the silylating agent, the silylation reaction is preferably allowed to proceed at 10 to 40 ° C. with sufficient stirring. If it is less than 10 ° C., the reaction hardly proceeds, and if it exceeds 40 ° C., it is not uniformly silylated on the nanodiamond surface. For example, when a hexane solution of triethylchlorosilane is used as a silylating agent, the hydroxyl group on the surface of the nanodiamond is sufficiently silyl-modified if the reaction is performed at 10 to 40 ° C. with stirring for about 10 to 40 hours.
［３］フッ素化処理
前記爆射法で得られた未精製のナノダイヤモンド、又は前記酸化処理により得られたナノダイヤモンドは、フルオロアルキル基含有オリゴマーを使用した方法、フッ素ガスと直接反応させる方法、フッ素プラズマによる方法等により、その表面をフッ素又はフッ素を有する基で修飾することができる。[3] Fluorination treatment The unpurified nanodiamond obtained by the explosion method or the nanodiamond obtained by the oxidation treatment is a method using a fluoroalkyl group-containing oligomer, a method of directly reacting with fluorine gas, The surface can be modified with fluorine or a fluorine-containing group by a method using fluorine plasma or the like.
（１）フルオロアルキル基含有オリゴマーを使用した方法
高分子主鎖の両末端にフルオロアルキル基が直接炭素−炭素結合により導入された高分子界面活性剤（含フッ素オリゴマー）は、水溶液中又は有機溶媒中において自己組織化したナノレベルの分子集合体を形成することが知られている。このフルオロアルキル基が末端に導入された含フッ素オリゴマーを用いることにより、フルオロアルキル基で修飾したナノダイヤモンドを形成することができる。(1) Method using a fluoroalkyl group-containing oligomer A polymer surfactant (fluorinated oligomer) in which a fluoroalkyl group is directly introduced into both ends of a polymer main chain by a carbon-carbon bond is used in an aqueous solution or an organic solvent. It is known to form nano-level molecular assemblies that are self-assembled therein. By using this fluorine-containing oligomer having a fluoroalkyl group introduced at the terminal, nanodiamonds modified with a fluoroalkyl group can be formed.
フルオロアルキル基で修飾したナノダイヤモンドは、爆射法で得られた未精製のナノダイヤモンド、又は前記酸化処理により得られたナノダイヤモンドを、一般式（１）で表される含フッ素オリゴマーで処理することによって得ることができる。 The nanodiamond modified with a fluoroalkyl group is treated with an unpurified nanodiamond obtained by an explosion method or a nanodiamond obtained by the oxidation treatment with a fluorine-containing oligomer represented by the general formula (1). Can be obtained.
ここで、ＲＦはフルオロアルキル基であり、具体的には、−ＣＦ（ＣＦ３）ＯＣ３Ｆ７、−ＣＦ（Ｃ３Ｆ）ＯＣＦ２ＣＦ（ＣＦ３）ＯＣ３Ｆ７等の基が好ましい。Ｒは置換基であり、−Ｎ（ＣＨ３）２、−ＯＨ、−ＮＨＣ（ＣＨ３）２ＣＨ２Ｃ（＝Ｏ）ＣＨ３、−Ｓｉ（ＯＣＨ３）３、−ＣＯＯＨ等の基が好ましい。ｎは５〜２０００であるのが好ましい。Here, R F is a fluoroalkyl group, specifically, a group such as —CF (CF 3 ) OC 3 F 7 , —CF (C 3 F) OCF 2 CF (CF 3 ) OC 3 F 7, etc. preferable. R is a substituent, and groups such as —N (CH 3 ) 2 , —OH, —NHC (CH 3 ) 2 CH 2 C (═O) CH 3 , —Si (OCH 3 ) 3 , —COOH are preferable. . n is preferably 5 to 2000.
ナノダイヤモンドと一般式（１）で表される含フッ素オリゴマーとをメタノール、エタノール等のアルコール溶媒中で混合し、室温〜８０℃で２〜４８時間撹拌することによりナノダイヤモンド表面にフルオロアルキル基（ＲＦ）が修飾された複合粒子を高い収率で得ることができる。反応を促進させるために、アンモニア等の塩基を使用してもよい。The nanodiamond and the fluorine-containing oligomer represented by the general formula (1) are mixed in an alcohol solvent such as methanol and ethanol, and stirred at room temperature to 80 ° C. for 2 to 48 hours to thereby add a fluoroalkyl group ( Composite particles modified with R F ) can be obtained in high yield. To accelerate the reaction, a base such as ammonia may be used.
（２）フッ素ガスと直接反応させる方法
フッ素ガスと直接反応させる方法は、ナノダイヤモンドを入れた反応管（ニッケル製等）に、フッ素ガスとアルゴン等の不活性ガスとの混合ガスを３００〜５００℃で１０〜５００時間流すことにより行う。(2) Method of directly reacting with fluorine gas The method of directly reacting with fluorine gas is a method of reacting a mixed gas of fluorine gas and an inert gas such as argon in a reaction tube (made of nickel, etc.) containing nano diamond. It is carried out by flowing at 10 ° C for 10 to 500 hours.
フッ素化ダイヤモンド微粒子のフッ素含有量は０．１〜２０ｗｔ％であるのが好ましく、０．２〜１５ｗｔ％であるのが好ましい。フッ素含有量が０．１ｗｔ％未満であると、フッ素含有の高分子樹脂を用いたとき、樹脂との相溶性が低下する。フッ素含有量が２０ｗｔ％以上であると、非フッ素系の溶剤や添加剤との相溶性が低下する。 The fluorine content of the fluorinated diamond fine particles is preferably 0.1 to 20 wt%, and preferably 0.2 to 15 wt%. When the fluorine content is less than 0.1 wt%, compatibility with the resin is reduced when a fluorine-containing polymer resin is used. When the fluorine content is 20 wt% or more, the compatibility with non-fluorinated solvents and additives decreases.
本発明を実施例によりさらに詳細に説明するが、本発明はそれらに限定されるものではない。 The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
実施例１
（１）ナノダイヤモンドの作製
ＴＮＴ（トリニトロトルエン）とＲＤＸ（シクロトリメチレントリニトロアミン）を６０／４０の比で含む０．６５ｋｇの爆発物を３ｍ３の爆発チャンバー内で爆発させて生成するＢＤを保存するための雰囲気を形成した後、同様の条件で２回目の爆発を起こしＢＤを合成した。爆発生成物が膨張し熱平衡に達した後、１５ｍｍの断面を有する超音速ラバルノズルを通して３５秒間ガス混合物をチャンバーより流出させた。チャンバー壁との熱交換及びガスにより行われた仕事（断熱膨張及び気化）のため、生成物の冷却速度は２８０℃／分であった。サイクロンで捕獲した生成物（黒色の粉末、ＢＤ）の比重は２．５５ｇ／ｃｍ３、メジアン径（動的光散乱法）は２２０ｎｍであった。このＢＤは比重から計算して、７６体積％のグラファイト系炭素と２４体積％のダイヤモンドからなっていると推定された。Example 1
(1) Production of nanodiamond BD produced by detonating 0.65 kg of explosives containing TNT (trinitrotoluene) and RDX (cyclotrimethylenetrinitroamine) in a ratio of 60/40 in a 3 m 3 explosion chamber After forming an atmosphere for storing the BD, a second explosion occurred under the same conditions to synthesize BD. After the explosion product expanded and reached thermal equilibrium, the gas mixture was allowed to flow out of the chamber for 35 seconds through a supersonic Laval nozzle having a 15 mm cross section. Due to the heat exchange with the chamber walls and the work done by the gas (adiabatic expansion and vaporization), the product cooling rate was 280 ° C./min. The specific gravity of the product (black powder, BD) captured by the cyclone was 2.55 g / cm 3 , and the median diameter (dynamic light scattering method) was 220 nm. This BD was calculated from specific gravity and was estimated to be composed of 76% by volume of graphite-based carbon and 24% by volume of diamond.
このＢＤを６０質量％硝酸水溶液と混合し、１６０℃、１４気圧、２０分の条件で酸化性分解処理を行った後、１３０℃、１３気圧、１時間で酸化性エッチング処理を行った。酸化性エッチング処理により、ＢＤからグラファイトが一部除去された粒子が得られた。この粒子を、アンモニアを用いて、２１０℃、２０気圧、２０分還流し中和処理した後、自然沈降させデカンテーションにより３５質量％硝酸での洗浄を行い、さらにデカンテーションにより３回水洗し、遠心分離により脱水し、１２０℃で加熱乾燥し、グラファイト相を有するナノダイヤモンドの粉末を得た。このナノダイヤモンドの粉末の比重は３．３８ｇ／ｃｍ３であり、メジアン径は５．５μｍ（動的光散乱法）であった。比重から計算して、９０体積％のダイヤモンドと１０体積％のグラファイト系炭素からなっていると推定された。This BD was mixed with a 60% by mass nitric acid aqueous solution, subjected to oxidative decomposition treatment at 160 ° C., 14 atm, and 20 minutes, and then oxidative etching treatment was performed at 130 ° C., 13 atm and 1 hour. Particles from which graphite was partially removed from BD were obtained by oxidative etching treatment. The particles were refluxed with ammonia at 210 ° C., 20 atm for 20 minutes, neutralized, then naturally settled, washed with 35 mass% nitric acid by decantation, and further washed with water three times by decantation. The powder was dehydrated by centrifugation and dried by heating at 120 ° C. to obtain nanodiamond powder having a graphite phase. The specific gravity of the nanodiamond powder was 3.38 g / cm 3 , and the median diameter was 5.5 μm (dynamic light scattering method). Calculated from the specific gravity, it was estimated to be composed of 90% by volume of diamond and 10% by volume of graphite-based carbon.
（２）ケイ素化処理
得られたナノダイヤモンドの粉末をメチルイソブチルケトンに３質量％の濃度で分散させ、トリメチルクロロシランのメチルイソブチルケトン溶液（濃度７．５質量％）を１：１の容量で加え、４８時間撹拌してナノダイヤモンドをトリメチルシランで修飾した。得られた分散物をメチルイソブチルケトンで洗浄後、乾燥し、トリメチルシラン修飾ナノダイヤモンド粉末を得た。(2) Siliconation treatment The obtained nanodiamond powder was dispersed in methyl isobutyl ketone at a concentration of 3% by mass, and a methyl isobutyl ketone solution of trimethylchlorosilane (concentration 7.5% by mass) was added at a volume of 1: 1. The nanodiamond was modified with trimethylsilane by stirring for 48 hours. The obtained dispersion was washed with methyl isobutyl ketone and then dried to obtain trimethylsilane-modified nanodiamond powder.
（３）摺動性樹脂部材の作製
樹脂部材として、ポリエチレンテレフタレート（ＰＥＴ、ＫＢセーレン社製、固有粘度０．６４）に得られたトリメチルシラン修飾ナノダイヤモンド粉末１０質量部を良く混練し、マスターチップを作製し、その後更にＰＥＴで希釈して、トリメチルシラン修飾ナノダイヤモンド粉末を１質量部含有のＰＥＴ固有粘度０．６１の名刺入れ（タテ×ヨコ×深さ；９．５ｃｍ×６ｃｍ×０．５ｃｍ）を得た。(3) Fabrication of slidable resin member As a resin member, 10 parts by mass of trimethylsilane-modified nanodiamond powder obtained from polyethylene terephthalate (PET, KB Selen Co., Ltd., intrinsic viscosity 0.64) was mixed well, and master chip After that, it is further diluted with PET, and a business card holder (vertical × horizontal × depth; 9.5 cm × 6 cm × 0.5 cm) having a PET intrinsic viscosity of 0.61 containing 1 part by mass of trimethylsilane-modified nanodiamond powder. )
（４）評価結果
添加剤の入っていない名刺入れ用ＰＥＴの作製は、１０回程度で成型加工機に付着し、離型性は悪かったが、本発明の樹脂は何回押出し成型しても、成型加工機への付着がなく、離型性が良好で、問題なく成型加工可能であった。摺動性を測る目安として、ＪＩＳ Ｋ７１２５に規定の方法で、静及び動摩擦係数を測定した。試料は、厚さ１００μのポリエチレンテレフタレート（ＰＥＴ）未延伸フイルム（Ａ）と、トリメチルシラン修飾ナノダイヤモンド粉末を１質量部含有の厚さ１００μのポリエチレンテレフタレート（ＰＥＴ）未延伸（Ｂ）を作製し、Ａ／Ａ、Ａ／Ｂ，Ｂ／Ｂ それぞれの静、動摩擦係数を測定した結果を表１に示す。
実施例２
（１）フッ素化処理
実施例１で作製したナノダイヤモンドの粉末を３質量％の濃度でメタノールに分散させ、下記式：Example 2
(1) Fluorination treatment The nanodiamond powder prepared in Example 1 was dispersed in methanol at a concentration of 3% by mass, and the following formula:
（ＲＦは−ＣＦ（ＣＦ３）ＯＣ３Ｆ７基、Ｒは−ＯＨ基、ｎは約８００である。）表される含フッ素オリゴマー、及び２８質量％アンモニア水を、ナノダイヤモンド分散物１００質量部に対してそれぞれ５０質量部及び１０質量部加え、８０℃で２０時間撹拌して反応させた。得られた分散物を中和、洗浄及び乾燥し、ナノダイヤモンド表面がフルオロアルキル基で修飾された複合粒子を得た。(R F is —CF (CF 3 ) OC 3 F 7 group, R is —OH group, and n is about 800.) 50 mass parts and 10 mass parts were added with respect to the mass part, respectively, and it was made to react by stirring at 80 degreeC for 20 hours. The obtained dispersion was neutralized, washed and dried to obtain composite particles in which the nanodiamond surface was modified with a fluoroalkyl group.
（２）摺動性樹脂部材の作製
トリメチルシラン修飾ナノダイヤモンド粉末の代わりに、フルオロアルキル基修飾ナノダイヤモンド粉末を使用した以外実施例１と同様にして、フルオロアルキル基修飾ナノダイヤモンド１質量部含有の径１０ｍｍの小型のＰＥＴ歯車を作製した。(2) Production of slidable resin member In the same manner as in Example 1 except that a fluoroalkyl group-modified nanodiamond powder was used instead of trimethylsilane-modified nanodiamond powder, 1 part by mass of fluoroalkyl group-modified nanodiamond was contained. A small PET gear with a diameter of 10 mm was produced.
（３）評価結果
添加剤の入っていない歯車の作製は、成型加工機に数回程度で成型加工機に付着し、離型性は悪かったが、本発明の樹脂は何回押出し成型しても、歯車の成型加工機への付着がなく、離型性が良好で、問題なく成型加工可能であった。実施例１と同様に、試料は、厚さ１００μのＰＥＴ未延伸フイルム（Ａ）と、フルオロアルキル基修飾ナノダイヤモンド粉末を１質量部含有の厚さ１００μのＰＥＴ未延伸（Ｂ）を作製し、Ａ／Ａ、Ａ／Ｂ，Ｂ／Ｂ それぞれの静、動摩擦係数を測定した結果を表２に示す。
実施例３
（１）摺動性樹脂部材の作製
実施例１で作製したトリメチルシラン修飾ナノダイヤモンド粉末、及び実施例２で作製したフルオロアルキル基修飾ナノダイヤモンド粉末を６：４の質量比となるよう混合した粉末を使用した以外実施例２と同様（１質量部）にして、径１０ｍｍの小型のＰＥＴ歯車を作製した。Example 3
(1) Production of sliding resin member Powder obtained by mixing trimethylsilane-modified nanodiamond powder produced in Example 1 and fluoroalkyl group-modified nanodiamond powder produced in Example 2 to a mass ratio of 6: 4 A small PET gear having a diameter of 10 mm was produced in the same manner as in Example 2 (1 part by mass) except that was used.
（２）評価結果
添加剤の入っていない歯車の作製は、成型加工機に１０回程度で成型加工機に付着し、離型性は悪かったが、本発明の樹脂は何回押出し成型しても、歯車の成型加工機への付着がなく、離型性が良好で、問題なく成型加工可能であった。、実施例１と同様に、試料は、厚さ１００μのＰＥＴ未延伸フイルム（Ａ）と、実施例３の修飾ナノダイヤモンド粉末含有の厚さ１００μのＰＥＴ未延伸（Ｂ）を作製し、Ａ／Ａ、Ａ／Ｂ，Ｂ／Ｂ それぞれの静、動摩擦係数を測定した結果を表３に示す。
実施例４
（１）ケイ素化及びフッ素化
実施例１で作製したトリメチルシラン修飾ナノダイヤモンド分散物を用いて、実施例２と同様にして、ナノダイヤモンド表面をフルオロアルキル基で修飾し、ナノダイヤモンド表面がトリメチルシラン及びフルオロアルキル基で修飾された複合粒子を得た。Example 4
(1) Siliconation and fluorination Using the trimethylsilane-modified nanodiamond dispersion prepared in Example 1, the nanodiamond surface was modified with a fluoroalkyl group in the same manner as in Example 2, and the nanodiamond surface was trimethylsilane. And composite particles modified with fluoroalkyl groups were obtained.
（２）摺動性樹脂部材の作製
トリメチルシラン修飾ナノダイヤモンド粉末の代わりに、トリメチルシラン及びフルオロアルキル基修飾ナノダイヤモンド粉末を使用した以外実施例２と同様（１質量部）にして、径１０ｍｍの小型のＰＥＴ歯車を作製した。(2) Production of slidable resin member The same procedure as in Example 2 (1 part by mass) except that trimethylsilane and fluoroalkyl group-modified nanodiamond powder were used instead of trimethylsilane-modified nanodiamond powder, and the diameter was 10 mm. A small PET gear was produced.
（３）評価結果
添加剤の入っていない歯車の作製は、成型加工機に１０回程度で成型加工機に付着し、離型性は悪かったが、本発明の樹脂は何回押出し成型しても、歯車の成型加工機への付着がなく、離型性が良好で、問題なく成型加工可能であった。実施例１と同様に、試料は、厚さ１００μのＰＥＴ未延伸フイルム（Ａ）と、実施例４の修飾ナノダイヤモンド粉末含有の厚さ１００μのＰＥＴ未延伸（Ｂ）を作製し、Ａ／Ａ、Ａ／Ｂ，Ｂ／Ｂ それぞれの静、動摩擦係数を測定した結果を表４に示す。
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| JP2012160947A Active JP5918054B2 (en) | 2012-07-03 | 2012-07-03 | A slidable resin member excellent in releasability comprising diamond fine particles having silicon and / or fluorine. |
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| JP2018140893A (en) * | 2017-02-28 | 2018-09-13 | 株式会社ダイセル | Surface-modified nanodiamond, dispersion containing the surface-modified nanodiamond, and composite material |
| WO2019146453A1 (en) * | 2018-01-29 | 2019-08-01 | 株式会社ダイセル | Nanodiamond particle dispersion |
| WO2020054337A1 (en) * | 2018-09-11 | 2020-03-19 | 株式会社ダイセル | Lubricant composition |
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| JP2018140893A (en) * | 2017-02-28 | 2018-09-13 | 株式会社ダイセル | Surface-modified nanodiamond, dispersion containing the surface-modified nanodiamond, and composite material |
| WO2019146453A1 (en) * | 2018-01-29 | 2019-08-01 | 株式会社ダイセル | Nanodiamond particle dispersion |
| CN111683899A (en) * | 2018-01-29 | 2020-09-18 | 株式会社大赛璐 | Nano-diamond particle dispersion |
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| JP7263260B2 (en) | 2018-01-29 | 2023-04-24 | 株式会社ダイセル | Nanodiamond particle dispersion |
| US11939222B2 (en) | 2018-01-29 | 2024-03-26 | Daicel Corporation | Nanodiamond particle dispersion |
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| JPWO2020054337A1 (en) * | 2018-09-11 | 2021-08-30 | 株式会社ダイセル | Lubricant composition |
| JP7451412B2 (en) | 2018-09-11 | 2024-03-18 | 株式会社ダイセル | lubricant composition |
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