JPWO2020129305A1 - Grease composition - Google Patents
Grease composition Download PDFInfo
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- JPWO2020129305A1 JPWO2020129305A1 JP2020515059A JP2020515059A JPWO2020129305A1 JP WO2020129305 A1 JPWO2020129305 A1 JP WO2020129305A1 JP 2020515059 A JP2020515059 A JP 2020515059A JP 2020515059 A JP2020515059 A JP 2020515059A JP WO2020129305 A1 JPWO2020129305 A1 JP WO2020129305A1
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- Prior art keywords
- fullerene derivative
- group
- grease composition
- formula
- fullerene
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000004519 grease Substances 0.000 title claims abstract description 40
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 40
- 239000003921 oil Substances 0.000 claims abstract description 28
- 239000002199 base oil Substances 0.000 claims abstract description 22
- 239000002562 thickening agent Substances 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910003472 fullerene Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005461 lubrication Methods 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 0 *c1cc(*)*(C=O)c(*)c1 Chemical compound *c1cc(*)*(C=O)c(*)c1 0.000 description 2
- BZBLUUDREZEDDJ-UHFFFAOYSA-N 2,2,3,3-tetrachloro-1,1,1,4,4,4-hexafluorobutane Chemical compound FC(F)(F)C(Cl)(Cl)C(Cl)(Cl)C(F)(F)F BZBLUUDREZEDDJ-UHFFFAOYSA-N 0.000 description 2
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N 2,4,6-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- GDSIBPPJKSBCMF-UHFFFAOYSA-N 1-(2,4,6-trihydroxyphenyl)ethanone;hydrate Chemical compound O.CC(=O)C1=C(O)C=C(O)C=C1O GDSIBPPJKSBCMF-UHFFFAOYSA-N 0.000 description 1
- WDIFKQOHZPTQIR-UHFFFAOYSA-N 2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-[1,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4,4-nonafluorobutoxy)ethoxy]ethoxy]ethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F WDIFKQOHZPTQIR-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M119/00—Lubricating compositions characterised by the thickener being a macromolecular compound
- C10M119/22—Lubricating compositions characterised by the thickener being a macromolecular compound containing halogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
Abstract
基油としてのパーフルオロポリエーテル油と、増ちょう剤と、パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体とを有し、前記基油１００質量部に対して、前記フラーレン誘導体を０．０００１〜０．２０００質量部含有するグリース組成物。It has a perfluoropolyether oil as a base oil, a thickener, and a fullerene derivative having a group containing a perfluoropolyether chain, and 0.0001 the fullerene derivative with respect to 100 parts by mass of the base oil. A grease composition containing up to 0.2000 parts by mass.
Description
本発明は、フッ素系グリース組成物に関する。 The present invention relates to a fluorinated grease composition.
近年、高速化、高効率化、高圧化及び小型化に伴い、自動車、工業機械等に使用される潤滑剤は、高圧、高速、高荷重及び高温度下で使用しても長時間にわたって充分に機械寿命を保証できる優れた潤滑性能が要求されている。このような状況下において、優れた熱安定性、低揮発性、耐薬品性、耐樹脂性および温度粘度特性を有する含フッ素系合成オイル、特にパーフルオロポリエーテル油は、潤滑組成物の基油として、注目を集めている。しかしながら、フッ素系合成オイルを基油とするフッ素系グリースは、エステル油や、合成炭化水素油等の合成油を基油とするグリースと比べて、金属とのなじみが悪く、耐摩耗性、耐焼付性について、一般的な合成油よりも劣っている。また、フッ素系グリースは油溶性に劣ることから、一般的な合成油に配合可能な汎用添加剤との相溶性が悪く、添加剤の添加による十分な耐摩耗性、耐焼付性を得ることが困難である。 In recent years, with the increase in speed, efficiency, high pressure and miniaturization, lubricants used in automobiles, industrial machines, etc. are sufficiently used for a long time even when used under high pressure, high speed, high load and high temperature. Excellent lubrication performance that can guarantee the machine life is required. Under such circumstances, fluorine-containing synthetic oils having excellent thermal stability, low volatility, chemical resistance, resin resistance and temperature viscosity characteristics, particularly perfluoropolyether oil, are the base oils of the lubricating composition. As, it is attracting attention. However, fluorine-based greases based on fluorosynthetic oils are less compatible with metals than greases based on synthetic oils such as ester oils and synthetic hydrocarbon oils, and have wear resistance and resistance. It is inferior to general synthetic oil in terms of seizure property. In addition, since fluorine-based grease is inferior in oil solubility, it has poor compatibility with general-purpose additives that can be blended in general synthetic oils, and sufficient abrasion resistance and seizure resistance can be obtained by adding the additives. Have difficulty.
特許文献１には、パーフルオロポリエーテル基油に、増ちょう剤として脂肪族ジカルボン酸金属塩、モノアミドモノカルボン酸金属塩またはモノエステルカルボン酸金属塩の少なくとも一種を添加してなる潤滑グリース組成物が開示されているが、潤滑特性を更なる改善が望まれる。 Patent Document 1 describes a lubricating grease composition obtained by adding at least one of an aliphatic dicarboxylic acid metal salt, a monoamide monocarboxylic acid metal salt, and a monoester carboxylic acid metal salt as a thickener to a perfluoropolyether base oil. Is disclosed, but further improvement in lubrication characteristics is desired.
また、特許文献２において、フッ素系基油に、リン酸塩、タングステン酸塩、硫酸塩および亜硫酸塩から選ばれる１種以上の無機酸塩を配合してなることを特徴とするグリース組成物が開示されているが、添加剤の凝集により、潤滑性能の劣化が懸念される。 Further, in Patent Document 2, a grease composition is characterized in that a fluorine-based base oil is blended with one or more inorganic acid salts selected from phosphates, tungstic acids, sulfates and sulfites. Although disclosed, there is concern about deterioration of lubrication performance due to aggregation of additives.
本発明者らは、以上の事情に鑑みてなされたものであり、十分な耐摩耗性を有するフッ素系グリース組成物を提供することを課題としている。 The present inventors have made this in view of the above circumstances, and an object of the present invention is to provide a fluorine-based grease composition having sufficient wear resistance.
本発明は、上記課題を解決するため、以下の［１］〜［５］を含む。
［１］ 基油としてのパーフルオロポリエーテル油と、増ちょう剤と、パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体とを有し、前記基油１００質量部に対して、前記フラーレン誘導体を０．０００１〜０．２０００質量部含有するグリース組成物。
［２］ 前記増ちょう剤はポリテトラフルオロエチレンである、前項［１］に記載のグリース組成物。
［３］ 前記フラーレン誘導体におけるパーフルオロポリエーテル鎖を含む基は、アリール基を有する接合構造を介して、フラーレン骨格に接合することを特徴とする前項［１］または前項［２］に記載のグリース組成物。
［４］ 前記フラーレン誘導体が、下記の式（１）または式（２）で表される構造を有する化合物から選択される少なくとも１種であることを特徴とする前項［１］〜［３］のいずれかに記載のグリース組成物。The present invention includes the following [1] to [5] in order to solve the above problems.
[1] A perfluoropolyether oil as a base oil, a thickener, and a fullerene derivative having a group containing a perfluoropolyether chain are provided, and the fullerene derivative is added to 100 parts by mass of the base oil. A grease composition containing 0.0001 to 0.2000 parts by mass.
[2] The grease composition according to the preceding item [1], wherein the thickener is polytetrafluoroethylene.
[3] The grease according to the preceding item [1] or the preceding item [2], wherein the group containing the perfluoropolyether chain in the fullerene derivative is bonded to the fullerene skeleton via a bonding structure having an aryl group. Composition.
[4] The above-mentioned items [1] to [3], wherein the fullerene derivative is at least one selected from compounds having a structure represented by the following formula (1) or formula (2). The grease composition according to any one.
（式中、ＦＬＮはフラーレン骨格を表し、Ａ１、Ａ２はそれぞれ独立にパーフルオロポリエーテル鎖を含む基を表し、Ｒ１、Ｒ２はそれぞれ独立に水素原子又は炭素数２４以下の炭化水素基を表す。なおａ、ｃはそれぞれ独立に２〜５の整数を表し、ｂ、ｄはそれぞれ独立に１〜５の整数を表す。）
［５］ 前記Ｒ１及びＲ２は、お互い独立して、炭素数２４以下のアルキル基又はアリール基である前項［４］に記載のグリース組成物。
(In the formula, FLN represents a fullerene skeleton, A 1 and A 2 each independently represent a group containing a perfluoropolyether chain, and R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon having 24 or less carbon atoms. A and c each independently represent an integer of 2 to 5, and b and d each independently represent an integer of 1 to 5.)
[5] The grease composition according to the preceding item [4], wherein R 1 and R 2 are alkyl groups or aryl groups having 24 or less carbon atoms independently of each other.
本発明によれば、耐摩耗性が優れたフッ素系グリース組成物を提供することができる。 According to the present invention, it is possible to provide a fluorine-based grease composition having excellent wear resistance.
以下、本発明の一実施形態を挙げて、詳細に説明する。なお、本発明はその要旨を変更しない範囲で適宜変更して実施することが可能である。 Hereinafter, an embodiment of the present invention will be described in detail. It should be noted that the present invention can be appropriately modified and implemented without changing the gist thereof.
本実施形態で得られるグリース組成物は、パーフルオロポリエーテル油からなる基油と、増ちょう剤と、パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体を含有し、基油１００質量部に対して、フラーレン誘導体の含有量は０．０００１〜０．２０００質量部である。 The grease composition obtained in the present embodiment contains a base oil composed of a perfluoropolyether oil, a thickener, and a fullerene derivative having a group containing a perfluoropolyether chain, with respect to 100 parts by mass of the base oil. The content of the fullerene derivative is 0.0001 to 0.2000 parts by mass.
本実施形態に係る基油として用いるパーフルオロポリエーテル油は、特に限定されるものではなく、通常公知のものは好適に用いられる。例えば、下記の一般式（ｉ）または（ｉｉ）の構造を有するものを用いることが可能である。
（ｉ） Ｒｆ１−Ｏ(ＣＦ２Ｏ)ｅ(Ｃ２Ｆ４Ｏ)ｆ〔ＣＦ（ＣＦ３）ＣＦ２Ｏ〕ｇ−Ｒｆ２（ここで、Ｒｆ１、Ｒｆ２は、それぞれ独立に炭素数１〜５のパーフルオロアルキル基を表す。なお、ｅ、ｆ、ｇは０または正の整数であり、かつ、ｅ＋ｆ＋ｇ＝２〜２００である）
（ｉｉ） Ｆ(ＣＦ２ＣＦ２ＣＦ２Ｏ)ｈＣ２Ｆ５
（ここで、ｈは２〜２００の整数を意味する。）
上記のパーフルオロポリエーテル油は、一種類を単独で使用しても良く、またこれらの中から選ばれる２種以上のものを任意の割合で混合して使用してもよい。
（増ちょう剤）
本実施形態に係るグリース組成物の増ちょう剤は、パーフルオロポリエーテルに分散し、半固体のグリース状にできるものであれば、用いることができる。例えば、金属石けん、ウレア化合物、フッ素樹脂等が挙げられる。耐熱性を考慮する場合、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロペン共重合体（ＦＥＰ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−エチレン共重合体（ＥＴＦＥ）、ポリビニリデンフルオライド（ＰＶＤＦ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、パーフルオロアルキレン樹脂等のフッ素樹脂が好ましく、その中で、フッ素系基油への分散性がよい点から、ポリテトラフルオロエチレン（ＰＴＦＥ）がより好ましい。また、これらの増ちょう剤は、一種類を単独で使用しても良く、２種以上を併用してもよい。なお、増ちょう剤の含有量は、所望のちょう度が得ればよいが、硬くなりすぎないように、基油１００質量部に対して、５０質量部未満であることが好ましく、４０質量部未満であることがより好ましい。
（フラーレン誘導体）
本発明の実施形態に係るフラーレン誘導体は、パーフルオロポリエーテル鎖を含む基を有するものである。The perfluoropolyether oil used as the base oil according to the present embodiment is not particularly limited, and generally known oils are preferably used. For example, one having the structure of the following general formula (i) or (ii) can be used.
(I) Rf 1 −O (CF 2 O) e (C 2 F 4 O) f [CF (CF 3 ) CF 2 O] g − Rf 2 (Here, Rf 1 and Rf 2 are independently carbon. Represents a perfluoroalkyl group of the number 1-5. Note that e, f, and g are 0 or a positive integer, and e + f + g = 2 to 200).
(Ii) F (CF 2 CF 2 CF 2 O) h C 2 F 5
(Here, h means an integer of 2 to 200.)
As the above-mentioned perfluoropolyether oil, one kind may be used alone, or two or more kinds selected from these may be mixed and used in an arbitrary ratio.
(Thickener)
The thickener of the grease composition according to the present embodiment can be used as long as it can be dispersed in perfluoropolyether to form a semi-solid grease. For example, metal soap, urea compound, fluororesin and the like can be mentioned. When considering heat resistance, both polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene Fluororesin such as polymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and perfluoroalkylene resin is preferable, and among them, the dispersibility in fluorobase oil is good. , Polytetrafluoroethylene (PTFE) is more preferred. Further, these thickeners may be used alone or in combination of two or more. The content of the thickener may be as long as the desired consistency can be obtained, but it is preferably less than 50 parts by mass and 40 parts by mass with respect to 100 parts by mass of the base oil so as not to become too hard. More preferably less than.
(Fullerene derivative)
The fullerene derivative according to the embodiment of the present invention has a group containing a perfluoropolyether chain.
本発明の実施形態に係るフラーレン誘導体中のフラーレン骨格としては、例えば、Ｃ６０、Ｃ７０、Ｃ７６、Ｃ７８、さらに高次のフラーレンが挙げられるが、潤滑油への溶解性の高さの点から、Ｃ６０及びＣ７０が好ましく、純度の高いものを工業的に容易に得る点と、潤滑油への着色が少ない点から、Ｃ６０がより好ましい。また、フラーレン誘導体のコストを低減するため、フラーレン誘導体の合成工程において、Ｃ６０とその他のフラーレンとの混合物であるミックスフラーレンを用いることもできる。ミックスフラーレンを使用する場合、Ｃ６０の質量割合が全体の５０％以上であることが好ましい。Examples of the fullerene skeleton in the fullerene derivative according to the embodiment of the present invention include C 60 , C 70 , C 76 , C 78 , and higher-order fullerenes, which have high solubility in lubricating oil. from the point, preferably C 60 and C 70, and that the obtained industrially easily a high purity, from the viewpoint coloring of the lubricating oil is small, C 60 is more preferable. Further, in order to reduce the cost of fullerene derivatives, in the synthesis process of the fullerene derivative, it is also possible to use a mix fullerene is a mixture of other fullerene C 60. When mixed fullerenes are used, the mass ratio of C 60 is preferably 50% or more of the total.
本発明のフラーレン誘導体が有するパーフルオロポリエーテル鎖を含む基のパーフルオロポリエーテル鎖の部分は、−（ＣＦ２）ｘＯ−（式中ｘは１〜５の整数である）で表される構造を有することが好ましい。さらに、−（ＣＦ２ＣＦ２Ｏ）ｙ（ＣＦ２Ｏ）ｚ−で表される部分構造を有することがより好ましい。ここで、ｙ及びｚは１〜５０の整数である。前記パーフルオロポリエーテル鎖を含む基の、パーフルオロポリエーテル鎖以外の部分は特に限定されない。前記パーフルオロポリエーテル鎖を含む基の末端部の構造としては、トリフルオロメチル基やパーフルオロブチル基などのパーフルオロアルキル基、メチル基やブチル基などのアルキル基、フェニル基やナフチル基などのアリール基、またはベンジル基やフェニルプロピル基などのアラルキル基を含む構造が好ましく、その中でもパーフルオロアルキル基がより好ましく、パーフルオロブチル基が特に好ましい。前記構造を有すると、フラーレン誘導体は、パーフルオロポリエーテル油への溶解性が向上する。The portion of the perfluoropolyether chain of the group containing the perfluoropolyether chain contained in the fullerene derivative of the present invention is represented by-(CF 2 ) x O- (x is an integer of 1 to 5 in the formula). It preferably has a structure. Further, it is more preferable to have a partial structure represented by − (CF 2 CF 2 O) y (CF 2 O) z −. Here, y and z are integers of 1 to 50. The portion of the group containing the perfluoropolyether chain other than the perfluoropolyether chain is not particularly limited. The structure of the terminal portion of the group containing the perfluoropolyether chain includes a perfluoroalkyl group such as a trifluoromethyl group and a perfluorobutyl group, an alkyl group such as a methyl group and a butyl group, and a phenyl group and a naphthyl group. A structure containing an aryl group or an aralkyl group such as a benzyl group or a phenylpropyl group is preferable, among which a perfluoroalkyl group is more preferable, and a perfluorobutyl group is particularly preferable. Having the above structure makes the fullerene derivative more soluble in perfluoropolyether oil.
なお、前記パーフルオロポリエーテル鎖を含む基は、直接的にフラーレン骨格に接合してもよく、接合構造を介して、フラーレン骨格に接合してもよい。接合構造について、特に限定されないが、アリール基を含む接合構造が好ましい。また、前記パーフルオロポリエーテル鎖を含む基は、直接的にアリール基と連結することがより好ましい。前記パーフルオロポリエーテル鎖を含む基のアリール基との連結部の構造としては、例えば、エーテル結合やエステル結合を含む構造が挙げられ、その中でもエーテル結合を含む構造が好ましく、特に−ＯＣＨ２−を含む構造が好ましい。The group containing the perfluoropolyether chain may be directly bonded to the fullerene skeleton, or may be bonded to the fullerene skeleton via a bonding structure. The bonding structure is not particularly limited, but a bonding structure containing an aryl group is preferable. Further, it is more preferable that the group containing the perfluoropolyether chain is directly linked to the aryl group. Examples of the structure of the linking portion of the group containing the perfluoropolyether chain with the aryl group include a structure containing an ether bond and an ester bond, and among them, a structure containing an ether bond is preferable, and particularly −OCH 2 −. A structure containing is preferable.
本発明のフラーレン誘導体は、特に以下の式（１）または式（２）の構造を有するものが最も好ましい。 The fullerene derivative of the present invention is most preferably one having the structure of the following formula (1) or formula (2).
（式中、ＦＬＮはフラーレン骨格を表し、Ａ１、Ａ２は、それぞれ独立にパーフルオロポリエーテル鎖を含む基を表し、Ｒ１、Ｒ２はそれぞれ独立に水素原子又は炭素数２４以下の炭化水素基を表す。また、ａ、ｃはそれぞれ独立に２〜５の整数を表し、ｂ、ｄはそれぞれ独立に１〜５の整数を表す。）
より具体的に、例えば、Ｒ１、Ｒ２としては、互いに独立に、水素原子、メチル基やエチル基などのアルキル基、フェニル基やナフチル基などのアリール基、ベンジル基やフェニルプロピル基などのアラルキル基が挙げられ、その中でもアルキル基またはアリール基であることが好ましく、メチル基またはフェニル基であることが特に好ましい。Ａ１、Ａ２としては、互いに独立に、−ＯＣＨ２（ＣＦ２Ｏ）ｍ（ＣＦ２ＣＦ２Ｏ）ｎＲ３で表されるものが挙げられる。ここで、Ｒ３としては、炭素数１〜５のアルキル基、パーフルオロアルキル基が挙げられ、その中でもパーフルオロアルキル基であることが好ましく、パーフルオロブチル基であることが特に好ましい。なお、ｍ、ｎはそれぞれ独立に１〜５０の整数を表す。本発明のフラーレン誘導体は上記の構造を有すれば、パーフルオロポリエーテル油への溶解性が高まる。
(In the formula, FLN represents a fullerene skeleton, A 1 and A 2 each independently represent a group containing a perfluoropolyether chain, and R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon having 24 or less carbon atoms. A and c each independently represent an integer of 2 to 5, and b and d each independently represent an integer of 1 to 5.)
More specifically, for example, R 1 and R 2 are independent of each other, such as a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group or a naphthyl group, a benzyl group or a phenylpropyl group. Examples thereof include an aralkyl group, of which an alkyl group or an aryl group is preferable, and a methyl group or a phenyl group is particularly preferable. Examples of A 1 and A 2 include those represented by −OCH 2 (CF 2 O) m (CF 2 CF 2 O) n R 3 independently of each other. Here, examples of R 3 include an alkyl group having 1 to 5 carbon atoms and a perfluoroalkyl group, and among them, a perfluoroalkyl group is preferable, and a perfluorobutyl group is particularly preferable. Note that m and n independently represent integers of 1 to 50. If the fullerene derivative of the present invention has the above structure, its solubility in perfluoropolyether oil is enhanced.
なお、上記式（１）または式（２）の構造を有するフラーレン誘導体は、ＷＯ２０１７／００６８１２号公報または特開２０１７−１４１９２号公報に記載の合成法により、作製することができる。 The fullerene derivative having the structure of the above formula (1) or formula (2) can be produced by the synthetic method described in WO2017 / 006812 or JP2017-14192.
本実施形態のグリース組成物のフラーレン誘導体の含有量は、基油１００質量部に対して、０．０００１〜０．２０００質量部であり、好ましくは０．００１０〜０．２０００質量部であり、より好ましくは０．００１０〜０．１０００質量部である。フラーレン誘導体の含有量が上記範囲内であれば、フラーレン誘導体は、パーフルオロポリエーテル油に溶解でき、十分な耐摩耗性向上の効果が期待できる。また、フラーレン誘導体の含有量は上記の範囲内であれば、高温、高圧の使用条件下においても、フラーレン誘導体の分解または凝集による固体物の生成が少なく、長時間にわたって、優れた潤滑性能を維持することができる。
（添加剤）
本実施形態のグリース組成物に、諸特性を改善するために、フラーレン誘導体以外の添加剤を更なる配合することができる。このような添加剤としては、特に限定されないが、例えば、市販の酸化防止剤、粘度指数向上剤、清浄分散剤、腐食防止剤、油性向上剤、錆止め添加剤、消泡剤、加水分解抑制剤などを配合することができる。The content of the fullerene derivative in the grease composition of the present embodiment is 0.0001 to 0.2000 parts by mass, preferably 0.0010 to 0.2000 parts by mass, based on 100 parts by mass of the base oil. More preferably, it is 0.0010 to 0.1000 parts by mass. When the content of the fullerene derivative is within the above range, the fullerene derivative can be dissolved in perfluoropolyether oil, and a sufficient effect of improving wear resistance can be expected. Further, if the content of the fullerene derivative is within the above range, even under high temperature and high pressure usage conditions, the formation of solid matter due to decomposition or aggregation of the fullerene derivative is small, and excellent lubrication performance is maintained for a long period of time. can do.
(Additive)
Additives other than fullerene derivatives can be further added to the grease composition of the present embodiment in order to improve various properties. Such additives are not particularly limited, but are, for example, commercially available antioxidants, viscosity index improvers, detergent dispersants, corrosion inhibitors, oiliness improvers, rust preventive additives, defoamers, and hydrolysis inhibitors. Etc. can be blended.
本発明のグリース組成物は、一般的なグリースの製造方法で作製できる。たとえば、パーフルオロポリエーテル油からなる基油にフラーレン誘導体、増ちょう剤、場合により、他の添加剤を添加し、適宜な装置で混練する方法を挙げることができるが、パーフルオロポリエーテル油からなる基油にフラーレン誘導体を溶解させた後に、増ちょう剤を添加することが好ましい。また、フラーレン誘導体を市販のパーフルオロポリエーテル系グリースに添加して、混合することにより、本発明のグリース組成物を得ることもできる。
（用途）
本実施形態のグリース組成物は、耐ガス性，低揮発性、高温特性、不燃性であることが特徴で、半導体真空ポンプ、高温ロール軸受、酸素ブロアー、電着塗装オーブン、フィルム延伸機 、ユルゲーター、複写機、レーザープリンター（ＬＢＰ）、コーン製造機、クリーンルーム、真空機器、遠心分離機各種バルブ、航空機器、宇宙機器などの各種用途に使用することができる。The grease composition of the present invention can be produced by a general method for producing grease. For example, a method of adding a fullerene derivative, a thickener, and in some cases other additives to a base oil composed of perfluoropolyether oil and kneading with an appropriate device can be mentioned, but from perfluoropolyether oil. It is preferable to add the thickener after dissolving the fullerene derivative in the base oil. Further, the grease composition of the present invention can also be obtained by adding a fullerene derivative to a commercially available perfluoropolyether-based grease and mixing them.
(Use)
The grease composition of the present embodiment is characterized by gas resistance, low volatility, high temperature characteristics, and nonflammability, and is characterized by a semiconductor vacuum pump, a high temperature roll bearing, an oxygen blower, an electrodeposition coating oven, a film stretching machine, and a urgator. , Copiers, laser printers (LBPs), cone making machines, clean rooms, vacuum equipment, centrifuge valves, aviation equipment, space equipment, etc.
以上、本発明の好ましい実施形態について述べたが、本発明は特定の実施の形態に限定されるものではなく、特許請求の範囲内に記載された本発明の要旨の範囲内において、種々の変形・変更が可能である。 Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the specific embodiments, and various modifications are made within the scope of the gist of the present invention described in the claims.・ Can be changed.
以下、本発明の実施例について説明する。なお、本発明は以下の実施例のみに限定されるものではない。
（ＮＭＲ分析）
１Ｈ−ＮＭＲは下記の条件にて測定した。
装置：日本電子製 ＪＮＭ−ＥＸ２７０
試料調製：試料（約１０ｍｇ〜３０ｍｇ）をＣＤＣｌ３／ヘキサフルオロベンゼン混合溶媒（約０．５ｍＬ）に溶解させた後、直径５ｍｍのＮＭＲ試料管に入れた。
測定温度：室温
基準物質：溶媒に添加されたテトラメチルシランのシグナルを基準とした。
（フラーレン誘導体Ａの合成）
フッ素化トリエチレングリコールモノブチルエーテル（化学式：ＣＦ３ＣＦ２ＣＦ２ＣＦ２（ＯＣＦ２ＣＦ２）２ＯＣＦ２ＣＨ２ＯＨ、Ｅｘｆｌｕｏｒ社製、１３ｇ、２４ｍｍｏｌ）、ピリジン（２．３ｇ、２９ｍｍｏｌ）をジクロロメタン（１２０ｍＬ）に加え、得られた溶液にトリフルオロメタンスルホン酸無水物（８．２ｇ、２９ｍｍｏｌ)のジクロロメタン（１２０ｍＬ）溶液を滴下した。室温で１６時間攪拌した後、反応混合物を純水（１００ｍＬ）と飽和炭酸ナトリウム水溶液（１００ｍＬ）で一度ずつ洗浄した。得られた有機層を濾過した後、ロータリーエバポレーターで濃縮することで、下記の式（３）の構造を有する化合物１（１５ｇ、２２ｍｍｏｌ、収率９２％）を淡黄色油状物質として得た。Hereinafter, examples of the present invention will be described. The present invention is not limited to the following examples.
(NMR analysis)
1 1 H-NMR was measured under the following conditions.
Equipment: JEM-EX270 manufactured by JEOL Ltd.
Sample preparation: A sample (about 10 mg to 30 mg) was dissolved in a mixed solvent of CDCl 3 / hexafluorobenzene (about 0.5 mL) and then placed in an NMR sample tube having a diameter of 5 mm.
Measurement temperature: Room temperature Reference substance: The signal of tetramethylsilane added to the solvent was used as a reference.
(Synthesis of fullerene derivative A)
Fluorinated triethylene glycol monobutyl ether (chemical formula: CF 3 CF 2 CF 2 CF 2 (OCF 2 CF 2 ) 2 OCF 2 CH 2 OH, Exfluor, 13 g, 24 mmol), pyridine (2.3 g, 29 mmol) in dichloromethane In addition to (120 mL), a solution of trifluoromethanesulfonic anhydride (8.2 g, 29 mmol) in dichloromethane (120 mL) was added dropwise to the obtained solution. After stirring at room temperature for 16 hours, the reaction mixture was washed once with pure water (100 mL) and saturated aqueous sodium carbonate solution (100 mL). The obtained organic layer was filtered and then concentrated on a rotary evaporator to obtain Compound 1 (15 g, 22 mmol, yield 92%) having the structure of the following formula (3) as a pale yellow oily substance.
上記で得た化合物１（６．５ｇ、１０ｍｍｏｌ）、２，４，６−トリヒドロキシベンズアルデヒド（０．４７ｇ、３．０ｍｍｏｌ）をＮ，Ｎ−ジメチルホルムアミド（６０ｍＬ）に加え、得られた溶液に炭酸セシウム（４．４ｇ、１４ｍｍｏｌ）を加えた。７０℃で２時間攪拌した後、反応混合物を室温まで冷やし、ロータリーエバポレーターで濃縮した。得られた混合物を純水（３０ｍＬ）とＡＫ―２２５（３０ｍＬ）を用いて分液し、さらに水層をＡＫ―２２５（２０ｍＬ）で二度抽出した。得られた有機層を水洗し、硫酸マグネシウムにより乾燥した。濾過した後、ロータリーエバポレーターで濃縮することで、赤褐色油状の粗生成物（５．２ｇ）を得た。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン―酢酸エチル（９：１））で精製することで、下記の式（４）の構造を有する化合物２を淡黄色油状物質（４．４ｇ、２．５ｍｍｏｌ、収率８３％）として得た。
Compound 1 (6.5 g, 10 mmol) and 2,4,6-trihydroxybenzaldehyde (0.47 g, 3.0 mmol) obtained above were added to N, N-dimethylformamide (60 mL) to the obtained solution. Cesium carbonate (4.4 g, 14 mmol) was added. After stirring at 70 ° C. for 2 hours, the reaction mixture was cooled to room temperature and concentrated on a rotary evaporator. The obtained mixture was separated using pure water (30 mL) and AK-225 (30 mL), and the aqueous layer was further extracted twice with AK-225 (20 mL). The obtained organic layer was washed with water and dried over magnesium sulfate. After filtration, the mixture was concentrated on a rotary evaporator to obtain a crude product (5.2 g) of reddish brown oil. By purifying with silica gel column chromatography (developing solvent: hexane-ethyl acetate (9: 1)), compound 2 having the structure of the following formula (4) was obtained as a pale yellow oily substance (4.4 g, 2.5 mmol, The yield was 83%).
上記で得た化合物２（４．４ｇ、２．５ｍｍｏｌ）とＮ−メチルグリシン（２．０ｇ、２３ｍｍｏｌ）をヘキサフルオロテトラクロロブタン（２０ｍＬ）に加え、得られた混合物にＣ６０（０．９５ｇ、１．３ｍｍｏｌ）のオルトジクロロベンゼン（４０ｍＬ）溶液を速やかに加えた。ジムロート冷却管を取り付け、１６０℃に設定した湯浴で加熱し、４時間攪拌しながら還流した。室温まで冷やした反応混合物をロータリーエバポレーターで濃縮した後に、適量のＡＫ―２２５に溶解させ濾過した。得られた溶液を純水（５０ｍＬ）で洗浄し、硫酸マグネシウムにより乾燥した。濾過した後、ロータリーエバポレーターで濃縮することで、黒色油状の粗生成物（４．１ｇ）を得た。
Compound 2 (4.4 g, 2.5 mmol) and N-methylglycine (2.0 g, 23 mmol) obtained above were added to hexafluorotetrachlorobutane (20 mL), and C 60 (0.95 g) was added to the obtained mixture. , 1.3 mmol) orthodichlorobenzene (40 mL) solution was added immediately. A Dimroth condenser was attached, and the mixture was heated in a hot water bath set at 160 ° C. and refluxed with stirring for 4 hours. The reaction mixture cooled to room temperature was concentrated on a rotary evaporator, dissolved in an appropriate amount of AK-225, and filtered. The obtained solution was washed with pure water (50 mL) and dried over magnesium sulfate. After filtration, the mixture was concentrated on a rotary evaporator to obtain a crude black oily product (4.1 g).
次に、入口および出口をもつ肉厚のステンレス容器（内径２０ｍｍ×深さ２００ｍｍ）に、粗生成物を入れ、容器内の温度を６０℃に保ちながら、超臨界二酸化炭素送液ポンプ（日本分光製、ＰＵ２０８６−ＣＯ２）を用いて、超臨界二酸化炭素を液化二酸化炭素換算流量５ｍＬ／分を容器に送った。容器内の圧力を１５〜２０ＭＰａの範囲で変化させ、黒色油状のフラーレン誘導体Ａを３．０ｇ抽出した。下記の式に示したＮＭＲの分析結果より、フラーレン誘導体Ａは以下式（５）の構造を有することが確認された。 Next, put the crude product in a thick stainless steel container (inner diameter 20 mm x depth 200 mm) with an inlet and an outlet, and keep the temperature inside the container at 60 ° C while supercritical carbon dioxide liquid feed pump (JASCO Corporation). , PU2086-CO2) was used to pump supercritical carbon dioxide to a container at a liquefied carbon dioxide equivalent flow rate of 5 mL / min. The pressure in the container was changed in the range of 15 to 20 MPa, and 3.0 g of the black oily fullerene derivative A was extracted. From the NMR analysis results shown in the following formula, it was confirmed that the fullerene derivative A has the structure of the following formula (5).
１Ｈ−ＮＭＲ δ（ｐｐｍ）：２．７９（ｂｒｓ、６Ｈ）、４．３９（ｂｒ、１８Ｈ）、６．２２（ｂｒｓ、４Ｈ）。 1 1 H-NMR δ (ppm): 2.79 (brs, 6H), 4.39 (br, 18H), 6.22 (brs, 4H).
（フラーレン誘導体Ｂの合成）
フラーレン誘導体Ａの合成と同様に化合物１を作製した。得た化合物１（８．２ｇ、１２ｍｍｏｌ）と、２'，４'，６'−トリヒドロキシアセトフェノン一水和物（０．５７ｇ、３．０ｍｍｏｌ）とをＮ，Ｎ−ジメチルホルムアミド（８０ｍＬ）に加え、得られた溶液に炭酸セシウム（５．９ｇ、１８ｍｍｏｌ）を加えた。７０℃で２時間攪拌した後、反応混合物を室温まで冷やし、ロータリーエバポレーターで濃縮した。得られた混合物を純水（３０ｍＬ）とＡＫ―２２５（３０ｍＬ）を用いて分液し、さらに水層をＡＫ―２２５（２０ｍＬ）で二度抽出した。得られた有機層を水洗し、硫酸マグネシウムにより乾燥した。濾過した後、ロータリーエバポレーターで濃縮することで、赤褐色油状の粗生成物（４．７ｇ）を得た。シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン―酢酸エチル（９：１））で精製することで、下記の式（６）の構造を有する化合物３を黄褐色油状物質（３．７ｇ、２．１ｍｍｏｌ、収率６９％）として得た。
(Synthesis of fullerene derivative B)
Compound 1 was prepared in the same manner as in the synthesis of the fullerene derivative A. The obtained compound 1 (8.2 g, 12 mmol) and 2', 4', 6'-trihydroxyacetophenone monohydrate (0.57 g, 3.0 mmol) were added to N, N-dimethylformamide (80 mL). In addition, cesium carbonate (5.9 g, 18 mmol) was added to the obtained solution. After stirring at 70 ° C. for 2 hours, the reaction mixture was cooled to room temperature and concentrated on a rotary evaporator. The obtained mixture was separated using pure water (30 mL) and AK-225 (30 mL), and the aqueous layer was further extracted twice with AK-225 (20 mL). The obtained organic layer was washed with water and dried over magnesium sulfate. After filtration, the mixture was concentrated on a rotary evaporator to obtain a crude product (4.7 g) of reddish brown oil. By purifying with silica gel column chromatography (developing solvent: hexane-ethyl acetate (9: 1)), compound 3 having the structure of the following formula (6) was obtained as a yellowish brown oily substance (3.7 g, 2.1 mmol, The yield was 69%).
上記で得た化合物４（３．６ｇ、１．９ｍｍｏｌ）とナトリウムメトキシド（０．１１ｇ、２．１ｍｍｏｌ）とをヘキサフルオロテトラクロロブタン（１０ｍＬ）とピリジン（１０ｍＬ）に加えた。得られた混合物を室温で３０分攪拌した後、Ｃ６０（０．７ｇ、０．９７ｍｍｏｌ）のオルトジクロロベンゼン（１００ｍＬ）溶液を速やかに加えた。ジムロート冷却管を取り付け、１８０℃に設定した湯浴で加熱し、１８時間攪拌しながら還流した。室温まで冷やした反応混合物をロータリーエバポレーターで濃縮し、反応溶媒を可能な限り取り除いた後に適量のＡＫ―２２５に溶解させ濾過し、未反応のフラーレンを除去した。得られた溶液を純水（５０ｍＬ）で洗浄し、硫酸マグネシウムにより乾燥した。濾過した後、ロータリーエバポレーターで濃縮することで、黒色油状の粗生成物（２．０ｇ）を得た。
Compound 4 (3.6 g, 1.9 mmol) and sodium methoxide (0.11 g, 2.1 mmol) obtained above were added to hexafluorotetrachlorobutane (10 mL) and pyridine (10 mL). The resulting mixture was stirred for 30 minutes at room temperature, C 60 (0.7g, 0.97mmol) was quickly added orthodichlorobenzene (100 mL) solution of. A Dimroth condenser was attached, and the mixture was heated in a hot water bath set at 180 ° C. and refluxed with stirring for 18 hours. The reaction mixture cooled to room temperature was concentrated on a rotary evaporator, the reaction solvent was removed as much as possible, and then dissolved in an appropriate amount of AK-225 and filtered to remove unreacted fullerenes. The obtained solution was washed with pure water (50 mL) and dried over magnesium sulfate. After filtration, it was concentrated on a rotary evaporator to obtain a crude product (2.0 g) of black oil.
次に、入口および出口をもつ肉厚のステンレス容器（内径２０ｍｍ×深さ２００ｍｍ）に、粗生成物を入れ、容器内の温度を６０℃に保ちながら、超臨界二酸化炭素送液ポンプ（日本分光製、ＰＵ２０８６−ＣＯ２）を用いて、超臨界二酸化炭素を液化二酸化炭素換算流量５ｍＬ／分を容器に送った。容器内の圧力を１２〜１８ＭＰａの範囲で変化させ、黒色油状のフラーレン誘導体Ｂを１．０ｇ抽出した。下記に示したＮＭＲの分析結果より、フラーレン誘導体Ｂは下記式（８）の構造を有することが確認された。 Next, put the crude product in a thick stainless steel container (inner diameter 20 mm x depth 200 mm) with an inlet and an outlet, and keep the temperature inside the container at 60 ° C while supercritical carbon dioxide liquid feed pump (JASCO Corporation). , PU2086-CO2) was used to pump supercritical carbon dioxide to a container at a liquefied carbon dioxide equivalent flow rate of 5 mL / min. The pressure in the container was changed in the range of 12 to 18 MPa, and 1.0 g of the black oily fullerene derivative B was extracted. From the NMR analysis results shown below, it was confirmed that the fullerene derivative B has the structure of the following formula (8).
１Ｈ−ＮＭＲ δ（ｐｐｍ）：２．６３（ｓ、３Ｈ）、４．４６（ｔ、４Ｈ）、４．６３（ｔ、２Ｈ）、６．３２（ｓ、２Ｈ）。 1 1 H-NMR δ (ppm): 2.63 (s, 3H), 4.46 (t, 4H), 4.63 (t, 2H), 6.32 (s, 2H).
(パーフルオロポリエーテル油)
パーフルオロポリエーテル油として、ＮＯＫ（株）製：ＢＲＡＡＩＥＲＴＡ Ｊ−１８０（Ｃ３Ｆ７Ｏ〔ＣＦ（ＣＦ３）ＣＦ２Ｏ〕ｊＣ２Ｆ５、ｊは２〜１００の整数である）
を用いる。
（実施例１）
基油として上記のＢＲＡＡＩＥＲＴＡ Ｊ−１８０ １００ｇに、フラーレン誘導体Ａを０．００１ｇ添加し、室温でスターラーを用いて３６時間撹拌して溶液を得た。得た溶液に、増ちょう剤としてポリテトラフルオロエチレン（ＰＴＦＥ）（喜多村（株）製 ＫＴＬ−８ＦＨ）を２０ｇ添加して、自転・公転ミキサー（シンキー社製、「あわとり練太郎」）で、１２００ｒｍｐで３分間予備混練したのち、３本ロールミルを用い、１．５ＭＰａ、０．４ＭＰａの圧力で２回混練処理を行い、グリース組成物を調製した。得たグリース組成物のフラーレン誘導体の含有量とＰＴＦＥの含有量は、基油１００質量部に対して、それぞれ０．００１０質量部と２０質量部である。なお、グリース組成物において、フラーレン誘導体の含有量とＰＴＦＥの含有量は、基油１００質量部に対して、それぞれの仕込み量より算出した。
（耐摩耗性評価）
ボールオンディスクトライボメーター（Ａｎｔｏｎｐａｒｒ製）試験により、得たグリース組成物の耐摩耗性を評価した。ボールとして、径６ｍｍ（ＳＵＪ２）、ディスクとして、径１３ｍｍ、厚さ５ｍｍ（ＳＵＪ２）をそれぞれ用い、荷重２Ｎ、回転速度１０ｒｐｍ、回転数１０００回の条件で摩耗痕径（ｍｍ）を測定した。本評価においては、摩耗痕径が小さいほど、摩耗特性に優れることを意味する
（実施例２〜１１、比較例１〜６）
増ちょう剤の含有量と、フラーレン誘導体の種類と、その含有量を表1の通りとした以外は、実施例１と同様にグリース組成物を調製し、表１に記載の荷重で耐摩耗性評価を実施した。なお、増ちょう剤の含有量、フラーレン誘導体の種類及びその含有量は、表１に記載の組成を有するグリース組成物となるようにそれぞれ調整した。
(Perfluoropolyether oil)
As a perfluoropolyether oil, manufactured by NOK Co., Ltd .: BRAAIERTA J-180 (C 3 F 7 O [CF (CF 3 ) CF 2 O] j C 2 F 5 , j is an integer of 2 to 100)
Is used.
(Example 1)
To 100 g of the above BRAAIERTA J-180 as a base oil, 0.001 g of fullerene derivative A was added, and the mixture was stirred at room temperature for 36 hours using a stirrer to obtain a solution. To the obtained solution, add 20 g of polytetrafluoroethylene (PTFE) (KTL-8FH manufactured by Kitamura Co., Ltd.) as a thickener, and use a rotation / revolution mixer (Sinky Co., Ltd., "Awatori Rentaro"). After pre-kneading at 1200 mp for 3 minutes, the grease composition was prepared by kneading twice at pressures of 1.5 MPa and 0.4 MPa using a 3-roll mill. The content of the fullerene derivative and the content of PTFE of the obtained grease composition are 0.0010 parts by mass and 20 parts by mass, respectively, with respect to 100 parts by mass of the base oil. In the grease composition, the content of the fullerene derivative and the content of PTFE were calculated from the respective charged amounts with respect to 100 parts by mass of the base oil.
(Abrasion resistance evaluation)
The wear resistance of the obtained grease composition was evaluated by a ball-on-disc tribometer (manufactured by Antonioparr) test. Using a ball having a diameter of 6 mm (SUJ2) and a disc having a diameter of 13 mm and a thickness of 5 mm (SUJ2), the wear mark diameter (mm) was measured under the conditions of a load of 2 N, a rotation speed of 10 rpm, and a rotation speed of 1000 times. In this evaluation, the smaller the wear mark diameter, the better the wear characteristics (Examples 2 to 11 and Comparative Examples 1 to 6).
A grease composition was prepared in the same manner as in Example 1 except that the content of the thickener, the type of the fullerene derivative, and the content thereof were as shown in Table 1, and the abrasion resistance was applied under the load shown in Table 1. Evaluation was carried out. The content of the thickener, the type of the fullerene derivative and the content thereof were adjusted so as to be a grease composition having the composition shown in Table 1.
本出願は２０１８年１２月２１日に出願した日本国特許出願第２０１８−２４００９９号に基づくものであり、その全内容は参照することによりここに組み込まれる。
This application is based on Japanese Patent Application No. 2018-240099 filed on December 21, 2018, the entire contents of which are incorporated herein by reference.
本発明は、上記課題を解決するため、以下の［１］〜［４］を含む。
［１］基油としての、パーフルオロポリエーテル油と、増ちょう剤と、フラーレン誘導体と、を有し、前記フラーレン誘導体が、式（１）
−ＯＣＨ ２ −Ｂ １ −Ｃ １
（式中、Ｂ １ は、式
−（ＣＦ ２ ） ｘ Ｏ−
（式中、ｘは、１〜５の整数である。）
で表される構造を有するパーフルオロポリエーテル鎖であり、Ｃ １ は、パーフルオロアルキル基、アルキル基、アリール基又はアラルキル基である。）
で表される基であり、Ｒ １ は、水素原子又は炭素数２４以下の炭化水素基であり、ａは、２〜５の整数であり、ｂは、１〜５の整数である。）
で表される化合物及び／又は式（２）
−ＯＣＨ ２ −Ｂ ２ −Ｃ ２
（式中、Ｂ ２ は、式
−（ＣＦ ２ ） ｘ Ｏ−
（式中、ｘは、１〜５の整数である。）
で表される構造を有するパーフルオロポリエーテル鎖であり、Ｃ ２ は、パーフルオロアルキル基、アルキル基、アリール基又はアラルキル基である。）
で表される基であり、Ｒ ２ は、水素原子又は炭素数２４以下の炭化水素基であり、ｃは、２〜５の整数であり、ｄは、１〜５の整数である。）
で表される化合物であり、前記基油１００質量部に対して、前記フラーレン誘導体を０．０００１〜０．２０００質量部含有する、グリース組成物。
［２］前記増ちょう剤は、ポリテトラフルオロエチレンである、前項［１］に記載のグリース組成物。
The present invention includes the following [1] to [ 4 ] in order to solve the above problems.
[1] as a base oil has a perfluoropolyether oil, and a thickener, a fullerene derivative, wherein the fullerene derivative has the formula (1)
-OCH 2- B 1- C 1
(In the formula, B 1 is the formula
-(CF 2 ) x O-
(In the formula, x is an integer from 1 to 5.)
It is a perfluoropolyether chain having a structure represented by, and C 1 is a perfluoroalkyl group, an alkyl group, an aryl group or an aralkyl group. )
Is a group represented by, R 1 is a hydrogen atom or a hydrocarbon group having 24 or less carbon atoms, a is an integer of 2 to 5, and b is an integer of 1 to 5. )
Compound represented by and / or formula (2)
-OCH 2- B 2- C 2
(In the formula, B 2 is the formula
-(CF 2 ) x O-
(In the formula, x is an integer from 1 to 5.)
It is a perfluoropolyether chain having a structure represented by, and C 2 is a perfluoroalkyl group, an alkyl group, an aryl group or an aralkyl group. )
Is a group represented by, R 2 is a hydrogen atom or a hydrocarbon group having 24 or less carbon atoms, c is an integer of 2 to 5, and d is an integer of 1 to 5. )
In a compound represented by, with respect to the base oil 100 parts by weight, the fullerene derivative containing 0.0001 to 0.2000 parts by weight, the grease composition.
[2] The thickener is polytetrafluoroethylene, the grease composition according to item [1].
［３］前記炭化水素基は、アルキル基又はアリール基である、前項［１］又は［２］に記載のグリース組成物。
［４］式（１）
−ＯＣＨ ２ −Ｂ １ −Ｃ １
（式中、Ｂ １ は、式
−（ＣＦ ２ ） ｘ Ｏ−
（式中、ｘは、１〜５の整数である。）
で表される構造を有するパーフルオロポリエーテル鎖であり、Ｃ １ は、パーフルオロアルキル基、アルキル基、アリール基又はアラルキル基である。）
で表される基であり、Ｒ １ は、水素原子又は炭素数２４以下の炭化水素基であり、ａは、２〜５の整数であり、ｂは、１〜５の整数である。）
で表される化合物及び／又は式（２）
−ＯＣＨ ２ −Ｂ ２ −Ｃ ２
（式中、Ｂ ２ は、式
−（ＣＦ ２ ） ｘ Ｏ−
（式中、ｘは、１〜５の整数である。）
で表される構造を有するパーフルオロポリエーテル鎖であり、Ｃ ２ は、パーフルオロアルキル基、アルキル基、アリール基又はアラルキル基である。）
で表される基であり、Ｒ ２ は、水素原子又は炭素数２４以下の炭化水素基であり、ｃは、２〜５の整数であり、ｄは、１〜５の整数である。）
で表される化合物である、グリース組成物用の添加剤。
[3] The hydrocarbon group is an A alkyl group or an aryl group, items [1] or grease composition as described in [2].
[4] Equation (1)
-OCH 2- B 1- C 1
(In the formula, B 1 is the formula
-(CF 2 ) x O-
(In the formula, x is an integer from 1 to 5.)
It is a perfluoropolyether chain having a structure represented by, and C 1 is a perfluoroalkyl group, an alkyl group, an aryl group or an aralkyl group. )
Is a group represented by, R 1 is a hydrogen atom or a hydrocarbon group having 24 or less carbon atoms, a is an integer of 2 to 5, and b is an integer of 1 to 5. )
Compound represented by and / or formula (2)
-OCH 2- B 2- C 2
(In the formula, B 2 is the formula
-(CF 2 ) x O-
(In the formula, x is an integer from 1 to 5.)
It is a perfluoropolyether chain having a structure represented by, and C 2 is a perfluoroalkyl group, an alkyl group, an aryl group or an aralkyl group. )
Is a group represented by, R 2 is a hydrogen atom or a hydrocarbon group having 24 or less carbon atoms, c is an integer of 2 to 5, and d is an integer of 1 to 5. )
An additive for a grease composition, which is a compound represented by.
Claims (5)
増ちょう剤と、
パーフルオロポリエーテル鎖を含む基を有するフラーレン誘導体とを有し、
前記基油１００質量部に対して、前記フラーレン誘導体を０．０００１〜０．２０００質量部含有するグリース組成物。Perfluoropolyether oil as a base oil and
Thickener and
With a fullerene derivative having a group containing a perfluoropolyether chain,
A grease composition containing 0.0001 to 0.2000 parts by mass of the fullerene derivative with respect to 100 parts by mass of the base oil.
（式中、ＦＬＮはフラーレン骨格を表し、Ａ１、Ａ２はそれぞれ独立にパーフルオロポリエーテル鎖を含む基を表し、Ｒ１、Ｒ２はそれぞれ独立に水素原子又は炭素数２４以下の炭化水素基を表す。なおａ、ｃはそれぞれ独立に２〜５の整数を表し、ｂ、ｄはそれぞれ独立に１〜５の整数を表す。）The grease according to any one of claims 1 to 3, wherein the fullerene derivative is at least one selected from compounds having a structure represented by the following formula (1) or formula (2). Composition.
(In the formula, FLN represents a fullerene skeleton, A 1 and A 2 each independently represent a group containing a perfluoropolyether chain, and R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon having 24 or less carbon atoms. A and c each independently represent an integer of 2 to 5, and b and d each independently represent an integer of 1 to 5.)
The grease composition according to claim 4, wherein R 1 and R 2 are alkyl groups or aryl groups having 24 or less carbon atoms independently of each other.
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