JP6028201B2 - Perfluoropolyether oil diffusion inhibitor and fluorine lubricant - Google Patents
Perfluoropolyether oil diffusion inhibitor and fluorine lubricant Download PDFInfo
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- JP6028201B2 JP6028201B2 JP2013112173A JP2013112173A JP6028201B2 JP 6028201 B2 JP6028201 B2 JP 6028201B2 JP 2013112173 A JP2013112173 A JP 2013112173A JP 2013112173 A JP2013112173 A JP 2013112173A JP 6028201 B2 JP6028201 B2 JP 6028201B2
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- perfluoropolyether
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- fluorine
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- 238000009792 diffusion process Methods 0.000 title claims description 123
- 239000003921 oil Substances 0.000 title claims description 114
- 239000003112 inhibitor Substances 0.000 title claims description 72
- 239000010702 perfluoropolyether Substances 0.000 title claims description 68
- 239000011737 fluorine Substances 0.000 title claims description 40
- 229910052731 fluorine Inorganic materials 0.000 title claims description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 37
- 239000000314 lubricant Substances 0.000 title description 26
- 239000000203 mixture Substances 0.000 claims description 57
- 239000004519 grease Substances 0.000 claims description 50
- 239000002199 base oil Substances 0.000 claims description 25
- 239000010687 lubricating oil Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 9
- 150000002222 fluorine compounds Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000002156 mixing Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000003405 preventing effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 230000000740 bleeding effect Effects 0.000 description 8
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002274 desiccant Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002545 silicone oil Polymers 0.000 description 5
- 229920001774 Perfluoroether Polymers 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- ZJFCVUTYZHUNSW-UHFFFAOYSA-N 3-octadecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCC1CC(=O)OC1=O ZJFCVUTYZHUNSW-UHFFFAOYSA-N 0.000 description 1
- HIJQFTSZBHDYKW-UHFFFAOYSA-N 4,4-dimethyloxane-2,6-dione Chemical compound CC1(C)CC(=O)OC(=O)C1 HIJQFTSZBHDYKW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C(N)=C(*)C(*)=*)=[O+] Chemical compound CC(C(N)=C(*)C(*)=*)=[O+] 0.000 description 1
- CUIWLCJMLNYOAV-UHFFFAOYSA-N CC(c1c(C(O)=O)c(C)c(C)c(C)c1C)=O Chemical compound CC(c1c(C(O)=O)c(C)c(C)c(C)c1C)=O CUIWLCJMLNYOAV-UHFFFAOYSA-N 0.000 description 1
- QDAWXRKTSATEOP-UHFFFAOYSA-N CC(c1ccccc1C(O)=O)=O Chemical compound CC(c1ccccc1C(O)=O)=O QDAWXRKTSATEOP-UHFFFAOYSA-N 0.000 description 1
- SGGDCHYGQZGONB-UHFFFAOYSA-N CCC(C)(CC(CC(C)=O)C([O]1(=C2C1)#C)=O)CC2(C)[N]#C Chemical compound CCC(C)(CC(CC(C)=O)C([O]1(=C2C1)#C)=O)CC2(C)[N]#C SGGDCHYGQZGONB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- KSDIHKMNSYWRFB-UHFFFAOYSA-N chrysen-2-amine Chemical compound C1=CC=CC2=CC=C3C4=CC=C(N)C=C4C=CC3=C21 KSDIHKMNSYWRFB-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は、パーフルオロポリエーテル油の拡散を防止する拡散防止剤、並びに、その拡散防止剤を含有したフッ素系潤滑剤に関する。 The present invention relates to a diffusion inhibitor that prevents diffusion of perfluoropolyether oil, and a fluorine-based lubricant containing the diffusion inhibitor.
グリースは、その基油や増ちょう剤により分類されることが多い。中でも、パーフルオロポリエーテル油をポリテトラフルオロエチレン等のフッ素系ポリマーや無機増ちょう剤により増ちょうさせたグリースをフッ素グリースと呼ぶ。フッ素グリースは、高価なものであるが、その基油に由来する優れた性能により、潤滑性、耐熱性、酸化安定性、対樹脂性、対ゴム性、低発塵性、耐薬品性といった非常に多機能を誇るグリースである。 Grease is often classified by its base oil and thickener. Among them, grease obtained by increasing perfluoropolyether oil with a fluorine-based polymer such as polytetrafluoroethylene or an inorganic thickener is called fluorine grease. Fluorine grease is expensive, but due to its excellent performance derived from its base oil, it has extremely high lubricity, heat resistance, oxidation stability, resistance to resin, resistance to rubber, low dust generation, and chemical resistance. It is a grease that boasts multiple functions.
このフッ素グリースは、特に、家電製品等の精密でデリケートな部分に使用されることが多い。家電製品は、製品によっては10年以上をノーメンテナンスで取り扱うため、フッ素グリースの多機能性は要求仕様を十分満足させうる。 This fluorine grease is often used particularly for precision and delicate parts such as home appliances. Since home appliances are handled with no maintenance for 10 years or more depending on the product, the multi-functionality of fluorine grease can sufficiently satisfy the required specifications.
ところが、上述のようにフッ素グリースは非常に多機能なグリースであるものの、汎用に使用される石鹸グリースに比べて、油拡散(油滲み)が大きいといった欠点を有している。この油拡散によって電気接点部位やレンズ部位に油が付着すると、作動不良等を起こす可能性がある。このような油拡散は、基油の粘度、基油と適用部材との濡れ性、適用部材の表面形状に大きく依存する。 However, as described above, although fluorine grease is a very multifunctional grease, it has a drawback that oil diffusion (oil bleeding) is larger than that of soap grease used for general purposes. If oil adheres to the electrical contact part or the lens part due to this oil diffusion, there is a possibility of causing malfunction or the like. Such oil diffusion largely depends on the viscosity of the base oil, the wettability between the base oil and the application member, and the surface shape of the application member.
グリースの油拡散防止に関する技術として、例えば特許文献1に記載の技術が知られている。この特許文献1には、合成潤滑油にフッ素系の界面活性剤を配合することによって、グリースからの滲み出し抑制を達成することが記載されている。しかしながら、ここで用いられる拡散防止剤は、パーフルオロポリエーテル油に対して効果が認められない。 As a technique related to prevention of oil diffusion of grease, for example, a technique described in Patent Document 1 is known. Patent Document 1 describes that suppression of exudation from grease is achieved by blending a synthetic surfactant with a fluorosurfactant. However, the diffusion inhibitor used here has no effect on perfluoropolyether oil.
一方、フッ素グリースの基油拡散防止策として、例えば特許文献2には、フッ素グリースにシリコーン油を0.1〜50重量%混合した非拡散性のフッ素グリース組成物が開示されている。しかしながら、パーフルオロポリエーテル油とシリコーン油とでは、相溶性がなく、また比重差が大きいことから、潤滑剤表面に対してシリコーン油のブリード現象、すなわち離しょうが大きくなる。また、潤滑性に乏しいシリコーン油を含むことから、特に金属対金属での耐荷重能が低下してしまい、その配合量によってはパーフルオロポリエーテル油の持つ耐荷重能を低下させてしまう。さらには、シリコーン油中の低分子量シロキサン成分が揮発して、接点障害を与える可能性があるため、接点部位には使用し難いといった問題がある。 On the other hand, for example, Patent Document 2 discloses a non-diffusible fluorine grease composition in which 0.1 to 50% by weight of silicone oil is mixed with fluorine grease as a base oil diffusion prevention measure for fluorine grease. However, since the perfluoropolyether oil and the silicone oil are not compatible and have a large specific gravity difference, the bleed phenomenon of the silicone oil, that is, the separation is increased with respect to the lubricant surface. Moreover, since the silicone oil with poor lubricity is included, the load bearing ability particularly in metal-to-metal is lowered, and depending on the blending amount, the load bearing ability of perfluoropolyether oil is lowered. Furthermore, since the low molecular weight siloxane component in the silicone oil volatilizes and may cause contact failure, there is a problem that it is difficult to use at the contact site.
このように、パーフルオロポリエーテル油の高い性能を維持しながら、油滲みを防止する技術は存在しない。パーフルオロポリエーテル油及びそのパーフルオロポリエーテル油を含有させたフッ素グリースの適用範囲は、各分野の発展と共に大きく拡がっており、高性能であり、且つ、油滲みの小さい潤滑剤が求められている。 Thus, there is no technique for preventing oil bleeding while maintaining the high performance of perfluoropolyether oil. The scope of application of perfluoropolyether oil and fluorine grease containing perfluoropolyether oil has greatly expanded with the development of each field, and there is a demand for a lubricant having high performance and low oil bleeding. Yes.
本発明は、このような従来の実情に鑑みて提案されたものであり、パーフルオロポリエーテル油及びフッ素グリースが有する高い性能を維持しつつ、そのパーフルオロポリエーテル油の拡散(油滲み)を小さくすることができるパーフルオロポリエーテル油の拡散防止剤、及びその拡散防止剤を含有したフッ素系潤滑剤を提供することを目的とする。 The present invention has been proposed in view of such a conventional situation, and the diffusion (oil bleeding) of the perfluoropolyether oil is maintained while maintaining the high performance of the perfluoropolyether oil and the fluorine grease. It is an object of the present invention to provide a perfluoropolyether oil diffusion inhibitor that can be made small, and a fluorine-based lubricant containing the diffusion inhibitor.
本発明者らは、上述した目的を達成するために鋭意検討を重ねた結果、所定のフッ素化合物が、パーフルオロポリエーテル油の性能を損ねることなく、そのパーフルオロポリエーテル油の滲みの抑制に有効に作用することを見出した。 As a result of intensive studies to achieve the above-described object, the present inventors have been able to suppress bleeding of the perfluoropolyether oil without deteriorating the performance of the perfluoropolyether oil. It was found that it works effectively.
すなわち、本発明に係るパーフルオロポリエーテル油の拡散防止剤は、下記化合物式(I)で表されるフッ素化合物を1種以上含有することを特徴とする。
CnF2n+1O(CF2CF2O)mCF2CH2O―R (I)
[式(I)中、n=1〜4、m=0〜2、Rは下記式(1)〜(22)
(式(1)中、n=0〜20である。)
C n F 2n + 1 O ( CF 2 CF 2 O) m CF 2 CH 2 O-R (I)
[In the formula (I), n = 1 to 4, m = 0 to 2, R represents the following formulas (1) to (22)
(In formula (1), n = 0 to 20.)
また、本発明に係る潤滑油組成物は、パーフルオロポリエーテル油に、上述の拡散防止剤を含有してなることを特徴とする。 Moreover, the lubricating oil composition according to the present invention is characterized in that the above-mentioned diffusion inhibitor is contained in perfluoropolyether oil.
また、本発明に係るグリース組成物は、基油であるパーフルオロポリエーテル油と、増ちょう剤とを含むグリースに、上述の拡散防止剤を含有してなることを特徴とする。 The grease composition according to the present invention is characterized in that the above-mentioned diffusion inhibitor is contained in a grease containing perfluoropolyether oil as a base oil and a thickener.
本発明に係る拡散防止剤によれば、パーフルオロポリエーテル油を含有したフッ素系潤滑剤の特性を損なわせることなく、油拡散(油滲み)を効果的に防止することができる。また、この拡散防止剤を含有させた潤滑油やグリースによれば、より万能な潤滑剤として様々な箇所に適用することができ、種々の製品に組み込んで長寿命の製品を提供することができる。 According to the diffusion inhibitor according to the present invention, oil diffusion (oil bleeding) can be effectively prevented without impairing the characteristics of the fluorine-based lubricant containing perfluoropolyether oil. Moreover, according to the lubricating oil or grease containing this diffusion inhibitor, it can be applied to various places as a more versatile lubricant, and can be incorporated into various products to provide a long-life product. .
以下、本発明に係る拡散防止剤、並びにその拡散防止剤を配合したフッ素系潤滑剤の具体的な実施形態(以下、「本実施の形態」という。)について詳細に説明する。なお、本発明は、以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲において変更が可能である。
1.拡散防止剤
2.潤滑剤組成物(潤滑油組成物、グリース組成物)
3.実施例
Hereinafter, a specific embodiment (hereinafter referred to as “this embodiment”) of a diffusion inhibitor according to the present invention and a fluorine-based lubricant containing the diffusion inhibitor will be described in detail. In addition, this invention is not limited to the following embodiment, In the range which does not change the summary of this invention, a change is possible.
1. Anti-diffusion agent Lubricant composition (lubricating oil composition, grease composition)
3. Example
≪1.拡散防止剤≫
(拡散防止剤の構成、並びに作用)
本実施の形態に係る拡散防止剤は、パーフルオロポリエーテル油を含むフッ素潤滑油又はパーフルオロポリエーテル油を増ちょう剤で増ちょうさせたフッ素グリース(以下、「潤滑剤」と総称することがある。)に添加して用いられるものであって、そのパーフルオロポリエーテル油の拡散を防止するためのものである。
<< 1. Diffusion inhibitor >>
(Configuration and action of diffusion inhibitor)
The diffusion preventing agent according to the present embodiment is a fluorine lubricant containing perfluoropolyether oil or a fluorine grease in which perfluoropolyether oil is increased with a thickener (hereinafter, collectively referred to as “lubricant”). In order to prevent diffusion of the perfluoropolyether oil.
具体的に、本実施の形態に係る拡散防止剤は、有効成分として下記化合物式(I)で表されるフッ素化合物を1種以上含有する。
CnF2n+1O(CF2CF2O)mCF2CH2O―R (I)
Specifically, the diffusion inhibitor according to the present embodiment contains one or more fluorine compounds represented by the following compound formula (I) as an active ingredient.
C n F 2n + 1 O ( CF 2 CF 2 O) m CF 2 CH 2 O-R (I)
ここで、上記化合物式(I)中において、n=1〜4、m=0〜2である。また、式(I)中のRは、下記式(1)〜(22)のうちの何れかの化合物を示す。
このような拡散防止剤によれば、上述したフッ素化合物を有効成分として含有することにより、パーフルオロポリエーテル油を含有したフッ素系潤滑剤の特性を損なわせることなく、油拡散(油滲み)を効果的に防止することができる。そして、この拡散防止剤を含有させた潤滑油やグリースは、より万能な潤滑剤として様々な箇所に適用することができる。具体的には、例えば家電製品等における電気接点部位やレンズ部位等の特に油滲みが問題となる部位に対しても、良好に適用することができる。このことから、種々の製品に組み込んで長寿命の製品を提供することが可能となる。 According to such a diffusion inhibitor, by containing the above-described fluorine compound as an active ingredient, oil diffusion (oil bleeding) can be achieved without impairing the characteristics of the fluorine-based lubricant containing perfluoropolyether oil. It can be effectively prevented. And the lubricating oil and grease containing this diffusion inhibitor can be applied to various places as a more versatile lubricant. Specifically, for example, the present invention can be favorably applied to a part where oil bleeding is a problem, such as an electrical contact part or a lens part in home appliances. Therefore, it is possible to provide a long-life product by being incorporated in various products.
(パーフルオロポリエーテル油(基油)、並びに油拡散のメカニズム)
ここで、基油としてのパーフルオロポリエーテル油は、例えば下記一般式(i)〜(iv)で表される構造を有するものを挙げることができる。具体的には、例えば、Krytoxシリーズ(イー・アイ・デュポン・ド・ヌムール・アンド・カンパニー製)、Fomblin Yシリーズ(ソルベイスペシャリティポリマーズジャパン製)、Fomblin Mシリーズ(ソルベイスペシャリティポリマーズジャパン製)、Fomblin Wシリーズ(ソルベイスペシャリティポリマーズジャパン製)、Fomblin Zシリーズ(ソルベイスペシャリティポリマーズジャパン製)、デムナムSシリーズ(ダイキン工業製)等の市販品を使用することができる。
(Perfluoropolyether oil (base oil) and oil diffusion mechanism)
Here, examples of the perfluoropolyether oil as the base oil include those having structures represented by the following general formulas (i) to (iv). Specifically, for example, Krytox series (manufactured by EI DuPont de Nemours & Company), Fomblin Y series (manufactured by Solvay Specialty Polymers Japan), Fomblin M series (manufactured by Solvay Specialty Polymers Japan), Fomblin W Commercial products such as series (manufactured by Solvay Specialty Polymers Japan), Fomblin Z series (manufactured by Solvay Specialty Polymers Japan), and demnum S series (manufactured by Daikin Industries) can be used.
F―(CFCF3―CF2―O―)n―CF2―CF3 (i)
(なお、式(i)中のnは、0又は正の整数。)
CF3―(O―CFCF3―CF2)p―(O―CF2―)q―O―CF3 (ii)
(なお、式(iii)中のp及びqは、それぞれ独立に、0又は正の整数。)
F―(CF2―CF2―CF2―O―)r―CF2―CF3 (iii)
(なお、式(iii)中のrは、0又は正の整数。)
CF3―(O―CF2―CF2―)s―(O―CF2―)t―O―CF3 (iv)
(なお、式(iv)中のs及びtは、それぞれ独立に、0又は正の整数。)
F— (CFCF 3 —CF 2 —O—) n— CF 2 —CF 3 (i)
(In the formula (i), n is 0 or a positive integer.)
CF 3- (O-CFCF 3 -CF 2 ) p- (O-CF 2- ) q -O-CF 3 (ii)
(Note that p and q in formula (iii) are each independently 0 or a positive integer.)
F- (CF 2 -CF 2 -CF 2 -O-) r -CF 2 -CF 3 (iii)
(In the formula (iii), r is 0 or a positive integer.)
CF 3- (O-CF 2 -CF 2- ) s- (O-CF 2- ) t -O-CF 3 (iv)
(Note that s and t in formula (iv) are each independently 0 or a positive integer.)
パーフルオロポリエーテル油の粘度は、油拡散に大きく影響を及ぼす因子である。粘度が高くなるとパーフルオロポリエーテル油自身の持つ低温性が悪くなってしまう。そのため、本実施の形態に係る拡散防止剤は、その粘度が40℃で10〜600mm2/sの範囲であるパーフルオロポリエーテル油に対して特に好適に用いることができる。また、パーフルオロポリエーテル油の化学構造については何ら縛られるものではなく、上述した直鎖タイプ及び側鎖タイプの両方に対して好適に用いることができる。 The viscosity of perfluoropolyether oil is a factor that greatly affects oil diffusion. When the viscosity increases, the low temperature property of the perfluoropolyether oil itself deteriorates. Therefore, the diffusion inhibitor according to the present embodiment can be particularly preferably used for perfluoropolyether oil having a viscosity of 10 to 600 mm 2 / s at 40 ° C. Further, the chemical structure of the perfluoropolyether oil is not restricted at all, and can be suitably used for both the above-mentioned linear type and side chain type.
基油として潤滑剤に含有させるパーフルオロポリエーテル油の拡散は、その基油が下地表面(潤滑剤適用箇所表面)の微小の粗さを介して毛細管現象によって伸び拡がることで生じるものと考えられる。ほとんどの下地表面には、少なからず粗さが存在するため、油拡散が嫌われる部位ではその拡散を効果的に防止することが必須となる。また、油の拡散距離は、油の粘性に大きく依存する。 The diffusion of perfluoropolyether oil contained in the lubricant as a base oil is considered to occur when the base oil expands and spreads by capillary action through the fine roughness of the base surface (the surface where the lubricant is applied). . Since most of the ground surface has a certain amount of roughness, it is essential to effectively prevent the diffusion at a site where oil diffusion is disliked. The oil diffusion distance greatly depends on the viscosity of the oil.
(油拡散防止のメカニズム)
本実施の形態に係る拡散防止剤は、以下のメカニズムにより油拡散を防止すると考えられる。すなわち、上述した拡散防止剤をパーフルオロポリエーテル油又はフッ素グリースに配合させると、その拡散防止剤が先行的に下地表面をコーティングする。このとき、拡散防止剤に含まれるフッ素化合物中のカルボキシル基やヒドロキシル基といった極性基が下地表面側に配向して、パーフルオロポリエーテル基が大気側を向く。一方で、パーフルオロポリエーテル油に残った拡散防止剤は、極性基が大気側を向くようなる。すると、この極性基が下地表面に先行してコーティングされたパーフルオロポリエーテル基と反発するようになり、これによってパーフルオロポリエーテル油の拡散を防ぐと考えられる。
(Oil diffusion prevention mechanism)
The diffusion inhibitor according to the present embodiment is considered to prevent oil diffusion by the following mechanism. That is, when the above-mentioned diffusion preventing agent is added to perfluoropolyether oil or fluorine grease, the diffusion preventing agent coats the base surface in advance. At this time, polar groups such as a carboxyl group and a hydroxyl group in the fluorine compound contained in the diffusion inhibitor are oriented on the base surface side, and the perfluoropolyether group faces the atmosphere side. On the other hand, in the diffusion inhibitor remaining in the perfluoropolyether oil, the polar group is directed to the atmosphere side. Then, it is considered that this polar group repels the perfluoropolyether group coated in advance on the base surface, thereby preventing the perfluoropolyether oil from diffusing.
(配合量)
この拡散防止剤の配合量としては、特に限定されるものではなく、パーフルオロポリエーテル油の化学構造や物性に応じて適宜決定することが好ましい。具体的には、例えば0.1〜10質量%程度の割合で配合することができる。なお、配合量が少なすぎると、油拡散の防止効果が十分に発現されない可能性があり、一方で配合量が多すぎると、拡散防止効果が頭打ちになるとともに、潤滑油成分の割合が少なくなるため潤滑性が低下する可能性がある。
(Mixing amount)
The blending amount of the diffusion inhibitor is not particularly limited, and is preferably determined appropriately according to the chemical structure and physical properties of the perfluoropolyether oil. Specifically, it can mix | blend in the ratio of about 0.1-10 mass%, for example. If the blending amount is too small, the oil diffusion preventing effect may not be sufficiently exhibited. On the other hand, if the blending amount is too large, the diffusion preventing effect reaches its peak and the ratio of the lubricating oil component decreases. Therefore, lubricity may be reduced.
上述したように、パーフルオロポリエーテル油の拡散はその粘度に依存する。そのため、基油として配合させたパーフルオロポリエーテル油の粘度に応じて拡散防止剤の配合量を変化させることが好ましい。一般的に、パーフルオロポリエーテル油は、その粘度が低いほど拡散しやすくなることから、拡散防止剤の配合量を多くする必要がある。この傾向を上述の拡散防止メカニズムに照らすと、潤滑剤を適用した下地の接触表面では、拡散防止剤の表面コーティングと基油の拡散が競争している状態となり、油の粘度が低いほど流動性がよくなるために拡散防止剤が表面をコーティングする前に基油拡散が起こる可能性がある。そのため、粘度が低いパーフルオロポリエーテル油の場合には、拡散防止剤の配合量を多くするように調整することが好ましい。 As mentioned above, the diffusion of perfluoropolyether oil depends on its viscosity. Therefore, it is preferable to change the blending amount of the diffusion inhibitor according to the viscosity of the perfluoropolyether oil blended as the base oil. In general, perfluoropolyether oil is more easily diffused as its viscosity is lower, so it is necessary to increase the amount of the diffusion inhibitor. In light of the above-mentioned diffusion prevention mechanism, the base contact surface to which the lubricant is applied is in a state where the surface coating of the diffusion prevention agent and the diffusion of the base oil compete with each other, and the lower the oil viscosity, the more fluid Base oil diffusion may occur before the diffusion inhibitor coats the surface. Therefore, in the case of a perfluoropolyether oil having a low viscosity, it is preferable to adjust so as to increase the amount of the diffusion inhibitor.
具体的に、例えば40℃における動粘度が100mm2/s未満のパーフルオロポリエーテル油の場合は、拡散防止剤を0.1〜10質量%程度の割合で配合させることが好ましく、0.1〜5.0質量%程度の割合で配合させることがより好ましい。また、40℃の基油の動粘度が100mm2/s以上のパーフルオロポリエーテル油の場合は、拡散防止剤を0.1〜5.0質量%程度の割合で配合させることが好ましく、0.1〜3.0質量%程度の割合で配合させることがより好ましい。 Specifically, for example, in the case of a perfluoropolyether oil having a kinematic viscosity at 40 ° C. of less than 100 mm 2 / s, it is preferable to add a diffusion inhibitor at a ratio of about 0.1 to 10% by mass. It is more preferable to mix them at a ratio of about ˜5.0% by mass. Further, in the case of a perfluoropolyether oil having a kinematic viscosity of 40 ° C. base oil of 100 mm 2 / s or more, it is preferable to add a diffusion inhibitor at a ratio of about 0.1 to 5.0% by mass. More preferably, it is blended at a ratio of about 1 to 3.0% by mass.
≪2.潤滑剤組成物(潤滑油組成物、グリース組成物)≫
(潤滑剤組成物について)
本実施の形態に係る潤滑剤組成物は、基油としてのパーフルオロエーテル油に、上述した拡散防止剤を含有してなるフッ素系潤滑剤組成物である。
≪2. Lubricant composition (lubricating oil composition, grease composition) >>
(About lubricant composition)
The lubricant composition according to the present embodiment is a fluorine-based lubricant composition comprising perfluoroether oil as a base oil containing the above-described diffusion inhibitor.
パーフルオロポリエーテル油としては、上述したように、一般式(i)〜(iv)で表される構造を有するものを挙げることができる。その中でも、粘度が40℃で10〜600mm2/sの範囲であるものを用いることが、より効果的に油拡散を防止できるという観点から好ましい。 Examples of the perfluoropolyether oil include those having structures represented by the general formulas (i) to (iv) as described above. Among them, it is preferable to use one having a viscosity of 10 to 600 mm 2 / s at 40 ° C. from the viewpoint that oil diffusion can be more effectively prevented.
フッ素グリース組成物とする場合、パーフルオロポリエーテル油を増ちょうさせる増ちょう剤としては、特に限定されるものではないが、ポリテトラフルオロエチレンを使用することが好ましい。ポリテトラフルオロエチレンは、パーフルオロポリエーテル油との親和性が高く、またそれ自身も高い潤滑性を有する。 When the fluorine grease composition is used, the thickener for increasing the perfluoropolyether oil is not particularly limited, but polytetrafluoroethylene is preferably used. Polytetrafluoroethylene has a high affinity with perfluoropolyether oil and itself has high lubricity.
その中でも、平均粒径が10.0μm以下のポリテトラフルオロエチレンを使用することが好ましい。ポリテトラフルオロエチレンの粒径が細かいほど、パーフルオロポリエーテル油との接触面積が大きくなるため、パーフルオロポリエーテル油の油分離を小さくする効果が認められる。平均粒径が10.0μmより大きい粒径のポリテトラフルオロエチレンを用いた場合、パーフルオロポリエーテル油との接触面積が小さくなり、すなわち親和力が小さくなる。そのため、同量配合した場合でも、平均粒径が10.0μm以下のものに比べて油分離が多く、またちょう度が大きくなり流動性が増すために適用部からの流出が起こり易くなる。ポリテトラフルオロエチレンの配合量を増やすことで、グリースのちょう度及び油分離量の低減は可能であるが、グリース中の固体成分比が大きくなってしまうため、グリースの粘性が増大し、ハンドリング及び低温下でのトルクが増大してしまう。このように、ポリテトラフルオロエチレンとしては、その粒径の細かいものほどパーフルオロポリエーテル油との親和力が大きくなるため好ましく、平均粒径が10.0μm以下、より好ましくは0.1μm〜5.0μmのものを使用する。 Among these, it is preferable to use polytetrafluoroethylene having an average particle size of 10.0 μm or less. As the particle size of the polytetrafluoroethylene is finer, the contact area with the perfluoropolyether oil becomes larger, so that the effect of reducing the oil separation of the perfluoropolyether oil is recognized. When polytetrafluoroethylene having an average particle size of more than 10.0 μm is used, the contact area with the perfluoropolyether oil is reduced, that is, the affinity is reduced. Therefore, even when the same amount is blended, oil separation is more than that having an average particle size of 10.0 μm or less, and the consistency is increased and the fluidity is increased. By increasing the blending amount of polytetrafluoroethylene, it is possible to reduce the consistency of the grease and the amount of oil separation, but since the ratio of solid components in the grease increases, the viscosity of the grease increases, handling and Torque at low temperatures will increase. Thus, as polytetrafluoroethylene, the finer the particle diameter, the greater the affinity with perfluoropolyether oil, which is preferable, and the average particle diameter is preferably 10.0 μm or less, more preferably 0.1 μm to 5. Use one with 0 μm.
また、上述したように、増ちょう剤としては、ポリテトラフルオロエチレンに限られるものではなく、パーフルオロポリエーテル油と親和性の高いものは好適に使用することができる。具体的には、例えば、ポリ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、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン−四フッ化エチレン共重合体、ポリビニリデンフルオライド等が挙げられる。また、その用途によっては、シリカエアロゲル、窒化ホウ素、窒化アルミニウム、炭酸カルシウム、リン酸カルシウム、酸化亜鉛、硫化亜鉛、タルク、グラファイト、二硫化モリブデン、メラニンシアヌル酸付加物、超高分子量ポリエチレン等の粉体を使用することもできる。 Further, as described above, the thickener is not limited to polytetrafluoroethylene, and those having high affinity with perfluoropolyether oil can be suitably used. Specifically, for example, polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride and the like can be mentioned. It is done. Depending on the application, powders such as silica aerogel, boron nitride, aluminum nitride, calcium carbonate, calcium phosphate, zinc oxide, zinc sulfide, talc, graphite, molybdenum disulfide, melanin cyanuric acid adduct, ultrahigh molecular weight polyethylene, etc. It can also be used.
(潤滑剤組成物の製造方法)
この潤滑剤組成物は、周知の一般的な方法により製造することができる。具体的には、例えばグリース組成物の場合、基油のパーフルオロエーテル油と増ちょう剤とを混練してグリース基剤を作製し、得られたグリース基剤に上述した拡散防止剤を所定量添加して分散させる。また、必要に応じて各種の添加剤を加えて混練する。これにより、拡散防止剤を配合させたグリース組成物を得ることができる。
(Method for producing lubricant composition)
This lubricant composition can be produced by a well-known general method. Specifically, for example, in the case of a grease composition, a grease base is prepared by kneading a perfluoroether oil of a base oil and a thickener, and a predetermined amount of the above diffusion inhibitor is added to the obtained grease base. Add and disperse. Further, various additives are added and kneaded as necessary. Thereby, the grease composition which mix | blended the diffusion inhibitor can be obtained.
潤滑油組成物の場合には、基油のパーフルオロエーテル油に拡散防止剤を所定量添加して攪拌する。また、必要に応じて各種の添加剤を加えて混練する。これにより、拡散防止剤を配合させた潤滑油組成物を得ることができる。 In the case of a lubricating oil composition, a predetermined amount of a diffusion inhibitor is added to the perfluoroether oil of the base oil and stirred. Further, various additives are added and kneaded as necessary. Thereby, the lubricating oil composition which mix | blended the diffusion inhibitor can be obtained.
混練処理や分散処理に際しては、例えば3本ロールミル、万能攪拌機、ホモジナイザー、コロイドミル等の周知の攪拌・分散処理装置を用いて行うことができる。なお、上述のように各成分を順に添加して混練することに限られず、各成分を同時に混練してもよい。 The kneading treatment or dispersion treatment can be performed using a known stirring / dispersing treatment apparatus such as a three-roll mill, a universal stirrer, a homogenizer, or a colloid mill. In addition, it is not restricted to adding each component in order and kneading | mixing as mentioned above, You may knead | mix each component simultaneously.
≪3.実施例≫
以下に本発明の優位性をより明確にする目的で、本発明を適用した実施例について説明するが、本発明は下記の実施例に限定されるものではない。
≪3. Examples >>
Examples for which the present invention is applied will be described below for the purpose of clarifying the superiority of the present invention. However, the present invention is not limited to the following examples.
<拡散防止剤>
本実施例において用いた拡散防止剤について以下に示す。なお、原料となるFluorinated triethylene glycol monobutyl etherは、Exfluor Research corp.社の製品を購入した。
<Diffusion inhibitor>
The diffusion inhibitor used in this example is shown below. In addition, Fluorinated triethylene monobutyl ether which is a raw material is Exfluor Research corp. The company's product was purchased.
[拡散防止剤A]
構造式:CF3CF2CF2CF2O(CF2CF2O)2CF2CH2OCOCH2CH2COOH
[Diffusion inhibitor A]
Structural formula: CF 3 CF 2 CF 2 CF 2 O (CF 2 CF 2 O) 2 CF 2 CH 2 OCOCH 2 CH 2 COOH
拡散防止剤Aは、以下のようにして合成した。すなわち、先ず、100mLナスフラスコに、攪拌子、Fluorinated triethylene glycol monobutyl ether(5.48g,10.0mmol)、コハク酸無水物(1.23g,12.3mmol)、ジクロロメタン(50mL)、トリエチルアミン(1.67mL,12.0mmol)を加え、45℃オイルバスで10時間還流した。次に、反応液にジクロロメタンを加えて分液漏斗に移し、1N塩酸、脱イオン水、飽和食塩水の順に洗浄(各2回)し、有機層に無水硫酸マグネシウムを加えて乾燥させた。そして、乾燥剤を濾別し、濾液をエバポレーターで濃縮して、拡散防止剤A(5.80g,8.95mmol,収率89%)を得た。 Anti-diffusion agent A was synthesized as follows. That is, first, in a 100 mL eggplant flask, a stir bar, fluorinated triethylene monobutyl ether (5.48 g, 10.0 mmol), succinic anhydride (1.23 g, 12.3 mmol), dichloromethane (50 mL), triethylamine (1. 67 mL, 12.0 mmol) was added, and the mixture was refluxed in an oil bath at 45 ° C. for 10 hours. Next, dichloromethane was added to the reaction solution, transferred to a separatory funnel, washed with 1N hydrochloric acid, deionized water, and saturated saline in this order (twice each), and anhydrous magnesium sulfate was added to the organic layer and dried. Then, the desiccant was filtered off, and the filtrate was concentrated with an evaporator to obtain diffusion inhibitor A (5.80 g, 8.95 mmol, yield 89%).
なお、プロトン核磁気共鳴分光法による測定を行った結果、上記構造式からなる化合物であることが確認された。測定結果を以下に示す。
1H−NMR(CDCl3,TMS,400MHz)δ=2.724(s,−CO−C2 H 4 −CO−),4.488(t,−CF2−CH 2 −O−)
As a result of measurement by proton nuclear magnetic resonance spectroscopy, it was confirmed that the compound had the above structural formula. The measurement results are shown below.
1 H-NMR (CDCl 3, TMS, 400MHz) δ = 2.724 (s, -CO-C 2 H 4 -CO -), 4.488 (t, -CF 2 -C H 2 -O-)
[拡散防止剤B]
構造式:CF3CF2CF2CF2O(CF2CF2O)2CF2CH2OCOCH2CH2CH2COOH
[Diffusion inhibitor B]
Structural formula: CF 3 CF 2 CF 2 CF 2 O (CF 2 CF 2 O) 2 CF 2 CH 2 OCOCH 2 CH 2 CH 2 COOH
拡散防止剤Bは、以下のようにして合成した。すなわち、先ず、窒素雰囲気下、100mLナスフラスコに、攪拌子、Fluorinated triethylene glycol monobutyl ether(8.35g,15.2mmol)、グルタル酸無水物(2.09g,18.3mmol)、クロロホルム(20mL、安定剤:アミレン)、トリエチルアミン(2.4mL,17.3mmol)を加え、還流管を取り付け60℃オイルバスで7時間ゆるやかに還流した。次に、反応液にジクロロメタンを加えて分液漏斗に移し、1N塩酸、脱イオン水、飽和食塩水の順に洗浄(各2回)し、有機層に無水硫酸マグネシウムを加えて乾燥させた。そして、乾燥剤を濾別し、濾液をエバポレーターで濃縮して、拡散防止剤B(9.12g, 13.8mmol,収率91%)を得た。 Anti-diffusion agent B was synthesized as follows. That is, first, in a 100 mL eggplant flask under a nitrogen atmosphere, a stirrer, fluorinated triethylene monobutyl ether (8.35 g, 15.2 mmol), glutaric anhydride (2.09 g, 18.3 mmol), chloroform (20 mL, stable) Agent: amylene) and triethylamine (2.4 mL, 17.3 mmol) were added, a reflux tube was attached, and the mixture was gently refluxed in a 60 ° C. oil bath for 7 hours. Next, dichloromethane was added to the reaction solution, transferred to a separatory funnel, washed with 1N hydrochloric acid, deionized water, and saturated saline in this order (twice each), and anhydrous magnesium sulfate was added to the organic layer and dried. Then, the desiccant was filtered off, and the filtrate was concentrated by an evaporator to obtain a diffusion inhibitor B (9.12 g, 13.8 mmol, yield 91%).
なお、プロトン核磁気共鳴分光法による測定を行った結果、上記構造式からなる化合物であることが確認された。測定結果を以下に示す。
1H−NMR(CDCl3,TMS,400MHz)δ=1.985(quin,−CO−CH2−CH 2 −CH2−CO−),2.452(t,−CO−CH2−CH2−CH 2 −COOH),2.510(t,−CO−CH 2 −CH2−CH2−COOH),4.471(t,−CF2−CH 2 −O−)
As a result of measurement by proton nuclear magnetic resonance spectroscopy, it was confirmed that the compound had the above structural formula. The measurement results are shown below.
1 H-NMR (CDCl 3, TMS, 400MHz) δ = 1.985 (quin, -CO-CH 2 -C H 2 -CH 2 -CO -), 2.452 (t, -CO-CH 2 -CH 2 -C H 2 -COOH), 2.510 (t, -CO-C H 2 -CH 2 -CH 2 -COOH), 4.471 (t, -CF 2 -C H 2 -O-)
[拡散防止剤C]
構造式:
Structural formula:
拡散防止剤Cは、以下のようにして合成した。すなわち、先ず、50mL二口フラスコに、攪拌子、Fluorinated triethylene glycol monobutyl ether(5.57g,10.2mmol)、3,3−ジメチルグルタル酸無水物(2.58g,18.2mmol)、クロロホルム(20mL、安定剤:アミレン)、トリエチルアミン(2.5mL,18.1mmol)を加え、60℃オイルバスで1日還流した。次に、反応液にクロロホルムを加えて分液漏斗に移し、1N塩酸、脱イオン水、飽和食塩水の順に洗浄(各3回)し、有機層に無水硫酸マグネシウムを加えて乾燥させた。そして、乾燥剤を濾別し、濾液をエバポレーターで濃縮して拡散防止剤C(5.20g,7.53mmol,収率74%)を得た。 Anti-diffusion agent C was synthesized as follows. That is, first, in a 50 mL two-necked flask, a stirrer, fluorinated triethylene monobutyl ether (5.57 g, 10.2 mmol), 3,3-dimethylglutaric anhydride (2.58 g, 18.2 mmol), chloroform (20 mL) Stabilizer: Amylene) and triethylamine (2.5 mL, 18.1 mmol) were added and refluxed in a 60 ° C. oil bath for 1 day. Next, chloroform was added to the reaction solution, transferred to a separatory funnel, washed with 1N hydrochloric acid, deionized water, and saturated saline in this order (3 times each), and dried over anhydrous magnesium sulfate. Then, the desiccant was filtered off, and the filtrate was concentrated by an evaporator to obtain a diffusion inhibitor C (5.20 g, 7.53 mmol, yield 74%).
なお、プロトン核磁気共鳴分光法による測定を行った結果、上記構造式からなる化合物であることが確認された。測定結果を以下に示す。
1H−NMR(CDCl3,TMS,400MHz)δ=1.145(s,−CH 3 ),2.477(s,−CO−CH2−C(CH3)2−CH 2 −COOH),2.565(s,−CO−CH 2 −C(CH3)2−CH2−COOH),4.456(t,−CF2−CH 2 −O−)
As a result of measurement by proton nuclear magnetic resonance spectroscopy, it was confirmed that the compound had the above structural formula. The measurement results are shown below.
1 H-NMR (CDCl 3, TMS, 400MHz) δ = 1.145 (s, -C H 3), 2.477 (s, -CO-CH 2 -C (CH 3) 2 -C H 2 -COOH ), 2.565 (s, -CO- C H 2 -C (CH 3) 2 -CH 2 -COOH), 4.456 (t, -CF 2 -C H 2 -O-)
[拡散防止剤D]
構造式:
Structural formula:
拡散防止剤Dは、以下のようにして合成した。すなわち、先ず、50mLナスフラスコに、攪拌子、Fluorinated triethylene glycol monobutyl ether(2.76g,5.03mmol)、オクタデシルコハク酸無水物(1.96g,5.57mmol)、クロロホルム(10mL、安定剤:アミレン)、トリエチルアミン(0.75mL,5.4mmol)を加え、室温で一日攪拌した。次に、反応液にクロロホルムを加えて分液漏斗に移し、1N塩酸、脱イオン水、飽和食塩水の順に洗浄(各2回)し、有機層に無水硫酸マグネシウムを加えて乾燥した。そして、乾燥剤を濾別し、濾液をエバポレーターで濃縮して、拡散防止剤D(3.37g,3.74mmol,収率74%)を得た。 The diffusion inhibitor D was synthesized as follows. That is, first, in a 50 mL eggplant flask, a stirrer, fluorinated triethylene monobutyl ether (2.76 g, 5.03 mmol), octadecyl succinic anhydride (1.96 g, 5.57 mmol), chloroform (10 mL, stabilizer: amylene) ), Triethylamine (0.75 mL, 5.4 mmol) was added, and the mixture was stirred at room temperature for one day. Next, chloroform was added to the reaction solution, transferred to a separatory funnel, washed with 1N hydrochloric acid, deionized water, and saturated saline in this order (twice each), and anhydrous magnesium sulfate was added to the organic layer and dried. Then, the desiccant was filtered off, and the filtrate was concentrated with an evaporator to obtain a diffusion inhibitor D (3.37 g, 3.74 mmol, yield 74%).
なお、プロトン核磁気共鳴分光法による測定を行った結果、上記構造式からなる化合物であることが確認された。測定結果を以下に示す。
1H−NMR(CDCl3,TMS,400MHz)δ=0.875(t,−CH 3 ),1.248(s,−CH2−(CH 2 )16−CH3),1.50〜1.75(m,−CH 2 −(CH2)16−CH3),2.45〜2.70(m,−CO−CH(C18H37)−CH 2 −COOH、及び、−CO−CH 2 −CH(C18H37)−COOH),4.35〜4.65(t,−CF2−CH 2 −O−)
As a result of measurement by proton nuclear magnetic resonance spectroscopy, it was confirmed that the compound had the above structural formula. The measurement results are shown below.
1 H-NMR (CDCl 3, TMS, 400MHz) δ = 0.875 (t, -C H 3), 1.248 (s, -CH 2 - (C H 2) 16 -CH 3), 1.50 ~1.75 (m, -C H 2 - (CH 2) 16 -CH 3), 2.45~2.70 (m, -CO-C H (C 18 H 37) -C H 2 -COOH, and, -CO-C H 2 -C H (C 18 H 37) -COOH), 4.35~4.65 (t, -CF 2 -C H 2 -O-)
[拡散防止剤E]
構造式:
Structural formula:
拡散防止剤Eは、以下のようにして合成した。すなわち、先ず、50mL二口フラスコに、攪拌子、Fluorinated triethylene glycol monobutyl ether(5.50g,10.0mmol)、フタル酸無水物(2.05g,13.8mmol)、クロロホルム(10mL、安定剤:アミレン)、トリエチルアミン(1.90mL,13.7mmol)を加え、90℃オイルバス中で一日還流した。次に、反応液にクロロホルムを加えて分液漏斗に移し、1N塩酸、脱イオン水、飽和食塩水の順に洗浄(各2回)し、有機層に無水硫酸マグネシウムを加えて乾燥させた。そして、乾燥剤を濾別し、濾液をエバポレーターで濃縮して、拡散防止剤E(5.04g,7.24mmol,収率72%)を得た。 The diffusion inhibitor E was synthesized as follows. That is, first, in a 50 mL two-necked flask, a stirrer, fluorinated triethylene monobutyl ether (5.50 g, 10.0 mmol), phthalic anhydride (2.05 g, 13.8 mmol), chloroform (10 mL, stabilizer: amylene) ), Triethylamine (1.90 mL, 13.7 mmol) was added, and the mixture was refluxed in a 90 ° C. oil bath for one day. Next, chloroform was added to the reaction solution, transferred to a separatory funnel, washed with 1N hydrochloric acid, deionized water, and saturated saline in this order (twice each), and dried over anhydrous magnesium sulfate. Then, the desiccant was filtered off, and the filtrate was concentrated by an evaporator to obtain a diffusion inhibitor E (5.04 g, 7.24 mmol, yield 72%).
なお、プロトン核磁気共鳴分光法による測定を行った結果、上記構造式からなる化合物であることが確認された。測定結果を以下に示す。
1H−NMR(CDCl3,TMS,400MHz)δ=4.678(t,−CF2−CH 2 −O−),7.60〜8.00(m,Aromatic)
As a result of measurement by proton nuclear magnetic resonance spectroscopy, it was confirmed that the compound had the above structural formula. The measurement results are shown below.
1 H-NMR (CDCl 3, TMS, 400MHz) δ = 4.678 (t, -CF 2 -C H 2 -O -), 7.60~8.00 (m, Aromatic)
[拡散防止剤F]
構造式:
Structural formula:
拡散防止剤F、以下のようにして合成した。すなわち、先ず、50mL三口フラスコに、攪拌子、Fluorinated triethylene glycol monobutyl ether(5.46g,9.96mmol)、cis−1,2−シクロヘキサンジカルボン酸無水物(1.91g,12.4mmol)、クロロホルム(15mL、安定剤:アミレン)、トリエチルアミン(1.90mL,13.7mmol)を加え、80℃オイルバス中で一日還流した。次に、反応液にクロロホルムを加えて分液漏斗に移し、1N塩酸、脱イオン水、飽和食塩水の順に洗浄(各3回)し、有機層に無水硫酸マグネシウムを加えて乾燥させた。そして、乾燥剤を濾別し、濾液をエバポレーターで濃縮して、拡散防止剤F(6.68g,9.52mmol,収率96%)を得た。 Diffusion inhibitor F was synthesized as follows. Specifically, first, a 50 mL three-necked flask was charged with a stirrer, fluorinated triethylene monobutyl ether (5.46 g, 9.96 mmol), cis-1,2-cyclohexanedicarboxylic anhydride (1.91 g, 12.4 mmol), chloroform ( 15 mL, stabilizer: amylene) and triethylamine (1.90 mL, 13.7 mmol) were added and refluxed in an 80 ° C. oil bath for one day. Next, chloroform was added to the reaction solution, transferred to a separatory funnel, washed with 1N hydrochloric acid, deionized water, and saturated saline in this order (3 times each), and dried over anhydrous magnesium sulfate. Then, the desiccant was filtered off, and the filtrate was concentrated by an evaporator to obtain a diffusion inhibitor F (6.68 g, 9.52 mmol, yield 96%).
なお、プロトン核磁気共鳴分光法による測定を行った結果、上記構造式からなる化合物であることが確認された。測定結果を以下に示す。
1H−NMR(CDCl3,TMS,400MHz)δ=1.35〜2.12(m,CH 2 in Cyclohexyl),2.905(s,(CH in Cyclohexyl)),4.30〜4.65(m,−CF2−CH 2 −O−)
As a result of measurement by proton nuclear magnetic resonance spectroscopy, it was confirmed that the compound had the above structural formula. The measurement results are shown below.
1 H-NMR (CDCl 3 , TMS, 400 MHz) δ = 1.35 to 2.12 (m, C H 2 in Cyclohexyl), 2.905 (s, (C H in Cyclohexyl)), 4.30-4 .65 (m, -CF 2 -C H 2 -O-)
<潤滑剤組成物>
実施例1〜24、比較例1〜3において、上述した拡散防止剤を下記表1〜3に示す配合割合にて含有させた潤滑剤組成物(グリース組成物、潤滑油組成物)を作製した。なお、配合量は「質量%」で表される。
<Lubricant composition>
In Examples 1 to 24 and Comparative Examples 1 to 3, a lubricant composition (grease composition, lubricating oil composition) containing the above-described diffusion inhibitor at a blending ratio shown in Tables 1 to 3 below was prepared. . The blending amount is represented by “mass%”.
ここで、基油となるパーフルオロポリエーテル油としては、ダイキン工業株式会社製のデムナムS−65を用いた。また、グリース組成物において、増ちょう剤としては、ポリテトラフルオロエチレン(イー・アイ・デュポン・ド・ヌムール・アンド・カンパニー製、ZONYL TLP 10F−1)を用いた。 Here, demnum S-65 manufactured by Daikin Industries, Ltd. was used as the perfluoropolyether oil serving as the base oil. In the grease composition, polytetrafluoroethylene (manufactured by EI DuPont de Nemours & Co., ZONYL TLP 10F-1) was used as a thickener.
フッ素グリース組成物(実施例1〜20)については、以下の方法により作製した。すなわち、パーフルオロポリエーテル油とポリテトラフルオロエチレンとを混練し、拡散防止剤を添加した後、3本ロールミルで分散処理を施して、各グリース組成物を作製した。一方、比較例1のフッ素グリース組成物は、パーフルオロポリエーテル油とポリテトラフルオロエチレンとを混練し、3本ロールミルで分散処理を施して、脱泡することで作製した。 The fluorine grease compositions (Examples 1 to 20) were produced by the following method. That is, perfluoropolyether oil and polytetrafluoroethylene were kneaded, a diffusion inhibitor was added, and then a dispersion treatment was performed with a three-roll mill to prepare each grease composition. On the other hand, the fluorine grease composition of Comparative Example 1 was prepared by kneading perfluoropolyether oil and polytetrafluoroethylene, performing dispersion treatment with a three-roll mill, and defoaming.
また、フッ素潤滑油組成物(実施例21〜24)については、以下の方法により作製した。すなわち、パーフルオロポリエーテル油に拡散防止剤を添加し、ディゾルバーを用いて攪拌することによって、各フッ素潤滑油組成物を作製した。なお、添加する拡散防止剤が固体状のものは100〜120℃で加熱溶解させて、ディゾルバーで攪拌してフッ素潤滑油組成物を作製した。一方、比較例2のフッ素潤滑油組成物は、パーフルオロポリエーテル油をそのまま用いた。 Moreover, about the fluorine lubricating oil composition (Examples 21-24), it produced with the following method. That is, each fluorine lubricating oil composition was prepared by adding a diffusion inhibitor to perfluoropolyether oil and stirring using a dissolver. A solid diffusion inhibitor was dissolved by heating at 100 to 120 ° C. and stirred with a dissolver to prepare a fluorine lubricating oil composition. On the other hand, the fluoro lubricating oil composition of Comparative Example 2 used perfluoropolyether oil as it was.
<拡散性試験、及び評価>
実施例1〜24にて作製した潤滑剤組成物について、油(パーフルオロエーテル油)拡散についての試験(拡散性試験)を行った。
<Diffusion test and evaluation>
About the lubricant composition produced in Examples 1-24, the test (diffusivity test) about oil (perfluoroether oil) spreading | diffusion was done.
油拡散試験としては、先ず、2000番目のラッピングペーパー上に各グリースを直径16mm、高さ2mmの円柱状に塗布し、60℃の恒温槽内で24時間放置して、円柱状のグリース外周部から外側に滲み出したオイルの短部までの平均距離を求めた。なお、パーフルオロポリエーテル油単体については、同様の試験において10μLを滴下した。そして、拡散防止剤を配合していない比較例1〜2(ブランク)と比較して、その油の拡散距離がどの程度低減できたかを評価することで行った。 In the oil diffusion test, first, each grease was applied to a 2000th wrapping paper in a cylindrical shape with a diameter of 16 mm and a height of 2 mm, and left in a constant temperature bath at 60 ° C. for 24 hours, and the outer periphery of the cylindrical grease The average distance from the oil to the short part of the oil oozing out was determined. In addition, about the perfluoropolyether oil simple substance, 10 microliters was dripped in the same test. And it compared with Comparative Examples 1-2 (blank) which is not mix | blending a diffusion inhibitor, and performed by evaluating how much the diffusion distance of the oil could be reduced.
なお、下記表1〜3に、それぞれの油拡散試験の結果と、油拡散防止効果の評価を示すが、その評価においては、ブランク(−)と比較して10%以上の拡散距離低減効果があったものを『○』、50%以上の低減効果があったものを『◎』とした。 In addition, although the result of each oil diffusion test and evaluation of the oil diffusion prevention effect are shown in Tables 1 to 3 below, in the evaluation, the diffusion distance reduction effect is 10% or more compared to the blank (-). The ones that were present were marked with “◯”, and those that had a reduction effect of 50% or more were marked with “◎”.
(実施例1〜11(拡散防止剤A〜Cを含有させたフッ素グリース組成物))
先ず、実施例1〜11として、基油であるパーフルオロポリエーテル油に上述の拡散防止剤A〜Cの何れかを所定の割合で配合させたフッ素グリース組成物における油拡散防止効果を試験した。下記表1に、グリースの組成と試験結果を示す。
(Examples 1 to 11 (fluorine grease composition containing diffusion inhibitors A to C))
First, as Examples 1 to 11, the oil diffusion preventing effect in a fluorine grease composition in which any of the above diffusion inhibitors A to C was blended in a predetermined ratio with perfluoropolyether oil as a base oil was tested. . Table 1 below shows the grease composition and test results.
表1に示されるように、拡散防止剤A〜Cの何れかを配合した実施例1〜11のフッ素グリース組成物では、拡散防止剤を配合していない比較例1(ブランク)と比較して、基油であるパーフルオロポリエーテル油の拡散を極めて効果的に抑制することが確認された。特に、その拡散防止剤を1.0質量%以上の配合割合とすることで、パーフルオロポリエーテル油がほぼ全く拡散することなく、効果的に油拡散を防止できることが確認された。 As shown in Table 1, in the fluorine grease compositions of Examples 1 to 11 in which any of the diffusion inhibitors A to C was blended, compared to Comparative Example 1 (blank) in which no diffusion inhibitor was blended It was confirmed that the diffusion of perfluoropolyether oil, which is a base oil, was extremely effectively suppressed. In particular, it was confirmed that by setting the diffusion inhibitor to a blending ratio of 1.0% by mass or more, the perfluoropolyether oil can be effectively prevented without substantially diffusing.
(実施例12〜20(拡散防止剤D〜Fを含有させたフッ素グリース組成物))
次に、実施例12〜20として、基油であるパーフルオロポリエーテル油に上述の拡散防止剤D〜Fの何れかを所定の割合で配合させたフッ素グリース組成物における油拡散防止効果を試験した。下記表2に、グリースの組成と試験結果を示す。
(Examples 12 to 20 (fluorine grease composition containing diffusion inhibitors D to F))
Next, as Examples 12 to 20, an oil diffusion preventing effect was tested in a fluorine grease composition in which any of the above diffusion inhibitors D to F was blended in a predetermined ratio with perfluoropolyether oil as a base oil. did. Table 2 below shows the grease composition and test results.
表2に示されるように、拡散防止剤D〜Fの何れかを配合した実施例12〜20のフッ素グリース組成物においても、拡散防止剤を配合していない比較例1(ブランク)と比較して、基油であるパーフルオロポリエーテル油の拡散を効果的に抑制することが確認された。 As shown in Table 2, the fluorine grease compositions of Examples 12 to 20 containing any of the diffusion inhibitors D to F were also compared with Comparative Example 1 (blank) containing no diffusion inhibitor. Thus, it was confirmed that the diffusion of perfluoropolyether oil as the base oil was effectively suppressed.
(実施例21〜24(フッ素潤滑油組成物についての試験))
次に、実施例21〜24として、基油であるパーフルオロポリエーテル油に上述の拡散防止剤Bを配合させたフッ素潤滑油組成物における油拡散防止効果を試験した。下記表3に、潤滑油の組成と試験結果を示す。
(Examples 21 to 24 (Test on Fluorine Lubricating Oil Composition))
Next, as Examples 21 to 24, the oil diffusion preventing effect in a fluorine lubricating oil composition in which the above-described diffusion inhibitor B was blended with perfluoropolyether oil as a base oil was tested. Table 3 below shows the composition and test results of the lubricating oil.
表3に示されるように、拡散防止剤を配合した実施例21〜24のフッ素潤滑油組成物では、拡散防止剤を配合していない比較例2(ブランク)と比較して、基油であるパーフルオロポリエーテル油の拡散を効果的に抑制することが確認された。特に、その拡散低減効果は、ブランクと比較してほぼ50%以上となり、拡散防止剤として有効に作用することが示された。 As shown in Table 3, in the fluorine lubricating oil compositions of Examples 21 to 24 blended with a diffusion inhibitor, it is a base oil compared to Comparative Example 2 (blank) that does not blend a diffusion inhibitor. It was confirmed that the diffusion of perfluoropolyether oil was effectively suppressed. In particular, the diffusion reduction effect is approximately 50% or more compared to the blank, and it was shown that it effectively acts as a diffusion inhibitor.
本発明に係る拡散防止剤によれば、パーフルオロポリエーテル油を基油とするフッ素グリースやフッ素系潤滑油に配合することによって、パーフルオロポリエーテル油の拡散を効果的に防止する拡散防止性能を付与することができる。これにより、パーフルオロポリエーテル油の高い性能を維持しつつ、従来成し得なかった油拡散の改善が可能となり、潤滑剤の油拡散が嫌われる部位(例えば電気接点部位やレンズ部位等)に対しても好適に用いることができ、良好な潤滑性能を発揮させることができる。 According to the anti-diffusion agent according to the present invention, the anti-diffusion performance that effectively prevents the perfluoropolyether oil from diffusing by blending with the fluorine grease or the fluorine-based lubricating oil based on the perfluoropolyether oil Can be granted. As a result, while maintaining the high performance of perfluoropolyether oil, it becomes possible to improve the oil diffusion that could not be achieved in the past, and to parts where oil diffusion of lubricants is disliked (for example, electrical contact parts and lens parts) Also, it can be suitably used, and good lubricating performance can be exhibited.
Claims (3)
CnF2n+1O(CF2CF2O)mCF2CH2O―R (I)
[式(I)中、n=1〜4、m=0〜2、Rは下記式(1)〜(22)
(式(1)中、n=0〜20である。)
C n F 2n + 1 O ( CF 2 CF 2 O) m CF 2 CH 2 O-R (I)
[In the formula (I), n = 1 to 4, m = 0 to 2, R represents the following formulas (1) to (22)
(In formula (1), n = 0 to 20.)
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