WO2015022871A9 - 含フッ素ポリエーテル化合物、潤滑剤、液状組成物および物品 - Google Patents
含フッ素ポリエーテル化合物、潤滑剤、液状組成物および物品 Download PDFInfo
- Publication number
- WO2015022871A9 WO2015022871A9 PCT/JP2014/070498 JP2014070498W WO2015022871A9 WO 2015022871 A9 WO2015022871 A9 WO 2015022871A9 JP 2014070498 W JP2014070498 W JP 2014070498W WO 2015022871 A9 WO2015022871 A9 WO 2015022871A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- group
- fluorine
- ocf
- containing polyether
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 457
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 175
- 229920000570 polyether Polymers 0.000 title claims abstract description 175
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 151
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000011737 fluorine Substances 0.000 title claims abstract description 126
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000007788 liquid Substances 0.000 title claims abstract description 56
- 239000000314 lubricant Substances 0.000 title claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 125000004185 ester group Chemical group 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000005647 linker group Chemical group 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 57
- 125000001153 fluoro group Chemical group F* 0.000 claims description 34
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 239000002904 solvent Substances 0.000 description 49
- 239000002344 surface layer Substances 0.000 description 46
- 239000010408 film Substances 0.000 description 37
- 229910052799 carbon Inorganic materials 0.000 description 30
- 239000012074 organic phase Substances 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 238000005481 NMR spectroscopy Methods 0.000 description 28
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 239000003960 organic solvent Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 150000001721 carbon Chemical group 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 16
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 150000007514 bases Chemical class 0.000 description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 150000001335 aliphatic alkanes Chemical group 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- -1 magnetic disks Substances 0.000 description 12
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 229910000104 sodium hydride Inorganic materials 0.000 description 10
- 239000012312 sodium hydride Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000012279 sodium borohydride Substances 0.000 description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 description 8
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000011775 sodium fluoride Substances 0.000 description 7
- 235000013024 sodium fluoride Nutrition 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- XAHBEACGJQDUPF-UHFFFAOYSA-N 1,2-dichloro-1,1,3,3,3-pentafluoropropane Chemical compound FC(F)(F)C(Cl)C(F)(F)Cl XAHBEACGJQDUPF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 0 C*1C=CC(C=C[*@](C2)C=[U]*#C)=C2C=C1 Chemical compound C*1C=CC(C=C[*@](C2)C=[U]*#C)=C2C=C1 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
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- 150000001450 anions Chemical class 0.000 description 3
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- 238000004128 high performance liquid chromatography Methods 0.000 description 3
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- 150000002576 ketones Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
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- 239000002798 polar solvent Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
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- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 3
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical group N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 2
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- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 125000005702 oxyalkylene group Chemical group 0.000 description 2
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 1
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 description 1
- XXZOEDQFGXTEAD-UHFFFAOYSA-N 1,2-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1C(F)(F)F XXZOEDQFGXTEAD-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- VXZBYIWNGKSFOJ-UHFFFAOYSA-N 2-[4-[5-(2,3-dihydro-1H-inden-2-ylamino)pyrazin-2-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC=1N=CC(=NC=1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 VXZBYIWNGKSFOJ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
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- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NEAPKZHDYMQZCB-UHFFFAOYSA-N N-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]ethyl]-2-oxo-3H-1,3-benzoxazole-6-carboxamide Chemical compound C1CN(CCN1CCNC(=O)C2=CC3=C(C=C2)NC(=O)O3)C4=CN=C(N=C4)NC5CC6=CC=CC=C6C5 NEAPKZHDYMQZCB-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910004013 NO 2 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000000560 X-ray reflectometry Methods 0.000 description 1
- IZZDJUXDSPENDV-UHFFFAOYSA-N [U]CC1C=Cc(cc(cccc2)c2c2)c2C=C1 Chemical compound [U]CC1C=Cc(cc(cccc2)c2c2)c2C=C1 IZZDJUXDSPENDV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000105 evaporative light scattering detection Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229950008618 perfluamine Drugs 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- JAJLKEVKNDUJBG-UHFFFAOYSA-N perfluorotripropylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F JAJLKEVKNDUJBG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010896 thin film analysis Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
- C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- 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
- C10M107/48—Lubricating compositions characterised by the base-material being a macromolecular compound containing phosphorus
-
- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
-
- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
- C10M2213/043—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen used as base material
-
- 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
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/0606—Perfluoro polymers used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/18—Electric or magnetic purposes in connection with recordings on magnetic tape or disc
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the present invention relates to a fluorine-containing polyether compound, a lubricant and a liquid composition containing the fluorine-containing polyether compound, and an article having a film made of the fluorine-containing polyether compound.
- the magnetic disk includes a base material, a magnetic recording layer formed on the surface of the base material, a carbon protective film formed on the surface of the magnetic recording layer, and a carbon protective film for the purpose of protecting the magnetic disk and the read head. It has a film (hereinafter also referred to as “surface layer”) formed by applying a lubricant to the surface.
- the surface layer is required to reduce the thickness of the surface layer and improve the lubricity of the surface layer. Further, as the information reading speed from the magnetic disk and the information writing speed to the magnetic disk are increased, the rotation of the magnetic disk is increasing. Therefore, the surface layer is required to improve the adhesion to the carbon protective film so as not to scatter from the magnetic disk rotating at high speed.
- the lubricant for forming the surface layer for example, the following are proposed.
- (1) It has four poly (oxyperfluoroalkylene) chains bonded to a tetravalent linking group, the chain consists only of (CF 2 CF 2 O) units, and HOCH 2 CH (OH ) Fluorinated polyether compound having a CH 2 OCH 2 CF 2 — group (Patent Document 1).
- JP 2009-197210 A Japanese Patent No. 5028801
- the fluorinated polyether compounds (1) and (2) having the chain are: Insufficient lubricity. Therefore, the lubricity of the surface layer formed from the fluorine-containing polyether compound cannot cope with the recent narrow distance between the magnetic disk and the read head.
- An object of the present invention is to provide a fluorine-containing polyether compound capable of forming a film having excellent lubricity, a lubricant and a liquid composition, and an article having a film having excellent lubricity on a substrate.
- the present invention provides a fluorine-containing polyether compound, a lubricant liquid composition and an article having the following configurations [1] to [13].
- X is a group having a hydroxyl group, a carboxy group, an ester group or an aryl group
- Y is a (m + n) -valent linking group having no etheric oxygen atom at the terminal; Z does not have a hydroxyl group, a carboxy group, an ester group or an aryl group, and a haloalkyl group (wherein the hal
- a group having a haloalkyl group (wherein the halogen atom is a fluorine atom or a chlorine atom), m is an integer from 1 to 10, n is an integer from 0 to 10, m + n is an integer from 2 to 20, a, b, c and d are each independently an integer of 1 to 100; [(CF 2 CF 2 O) a - (CF 2 CF 2 CF 2 CF 2 O) b] of a number in (CF 2 CF 2 O) units and a number b of (CF 2 CF 2 CF 2 CF 2 O ) units of the binding order, and, [(OCF 2 CF 2) c - (OCF 2 CF 2 CF 2 CF 2) d] in c-number of the (OCF 2 CF 2) units and d pieces of (OCF 2 CF 2
- the bonding order of the CF 2 CF 2 ) units is not limited.
- [2] The fluorine-containing polyether compound of [1], which has a number average molecular weight of 500 to 50,000.
- [3] The fluorine-containing polyether compound of [1] or [2], wherein b / (a + b) is 0.2 to 0.8 and d / (c + d) is 0.2 to 0.8.
- [4] The fluorinated polyether compound according to any one of [1] to [3], which has a structure in which (OCF 2 CF 2 ) units and (OCF 2 CF 2 CF 2 CF 2 ) units are alternately arranged.
- X is a group having a hydroxyl group, a carboxy group, an ester group or an aryl group
- W represents a hydroxyl group, a carboxy group, an ester group, an aryl group, a haloalkyl group (where a halogen atom is a fluorine atom or a chlorine atom), or a haloalkyl group in which an etheric oxygen atom is inserted between carbon atoms.
- g and h are each independently an integer of 1 to 200; [(CF 2 CF 2 O) g - (CF 2 CF 2 CF 2 CF 2 O) h] in g-number of the (CF 2 CF 2 O) units and h pieces of (CF 2 CF 2 CF 2 CF 2 O )
- the order of unit binding is not limited.
- a lubricant comprising the fluorine-containing polyether compound of any one of [1] to [10].
- a liquid composition comprising the fluorinated polyether compound of any one of [1] to [10] and a liquid medium.
- a film having excellent lubricity can be formed.
- the article of the present invention has a film having excellent lubricity on a substrate.
- alkane group means a monovalent or higher group obtained by removing one or more hydrogen atoms from an alkane.
- the monovalent alkane group is an alkyl group
- the divalent alkane group is an alkylene group.
- Perfluoro means that all of the hydrogen atoms bonded to the carbon atom are replaced with fluorine atoms.
- fluoroalkane group means a group in which part or all of the hydrogen atoms of the alkane group are substituted with fluorine atoms.
- perfluoroalkane group means a group in which all of the hydrogen atoms of the alkane group are substituted with fluorine atoms.
- haloalkyl group means a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, chlorine atoms, or both.
- fluoroalkyl group means a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
- esteer group means a group represented by RC (O) O— or ROC (O) — (wherein R is a hydrocarbon group).
- etheric oxygen atom means an oxygen atom that forms an ether bond (—O—) between carbon atoms.
- polyether chain is a chain in which a plurality of oxyalkylene groups (however, some or all of the hydrogen atoms of the alkylene group may be substituted with fluorine atoms, chlorine atoms, or both) are connected.
- Means a divalent group of the structure “Polyether chain” includes poly (oxyalkylene) groups, poly (oxyfluoroalkylene) groups, poly (oxyperfluoroalkylene) groups, and the like.
- the first aspect of the fluorinated polyether compound of the present invention is a fluorinated polyether compound (A) represented by the following formula (A) (hereinafter also referred to as compound (A)).
- A fluorinated polyether compound represented by the following formula (A) (hereinafter also referred to as compound (A)).
- X is a group having a hydroxyl group, a carboxy group, an ester group or an aryl group.
- the number m of the groups having X is an integer of 1 to 10, and 1 to 6 is preferable from the viewpoint of excellent solubility of the compound (A) in a solvent, viscosity, and lubricity.
- Examples of X include a group (X1) represented by the following formula (X1). (X 1 ) i -Q 1- (X1) However, X 1 is a hydroxyl group, a carboxy group, an ester group or an aryl group, Q 1 is a (i + 1) -valent linking group (provided that when it does not have an oxygen atom bonded to the adjacent oxygen atom on the right side and X 1 is a hydroxyl group or an RC (O) O— group, it binds to these) Does not have an oxygen atom). i is 1 or 2.
- Examples of the group (X1) include a group (X11) represented by the following formula (X11), a group (X12) represented by the following formula (X12), and a group (X13) represented by the following formula (X13).
- Q F is —CF 2 — or —CF 2 CF 2 CF 2 —
- Q 11 is an (i + 1) -valent alkane group (alkylene group, alkane-triyl group) or an (i + 1) -valent alkane group in which an etheric oxygen atom is inserted between carbon atoms and carbon atoms
- Q 12 is a single bond, —C (O) —, —NH—, an alkylene group or an alkylene group having an etheric oxygen atom inserted between carbon atoms and carbon atoms
- Q 12 is a single bond, —C (O) —, —NH—, an alkylene group or an alkylene group having an etheric oxygen atom inserted between carbon
- Examples of the group (X11) include the following groups. HOCH 2 CF 2 CF 2 CF 2- HOCH 2 CF 2- HOCH 2 CH 2 CF 2 CF 2 CF 2- HOCH 2 CH 2 CF 2-
- Examples of the group (X12) include the following groups. HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2- HOCH 2 CH (OH) CH 2 OCH 2 CF 2- HOCH 2 CH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2- HOCH 2 CH 2 CH (OH) CH 2 OCH 2 CF 2- HOCH 2 CH 2 CH (OH) CH 2 OCH 2 CF 2- HOCH 2 CH 2 CH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2- HOCH 2 CH 2 CH 2 CH (OH) CH 2 OCH 2 CF 2- HOCH 2 CH 2 OCH 2 CF 2- HOCH 2 CH 2 OCH 2 CF 2- HOCH 2 CH 2 OCH 2 CF 2- HOCH 2 CH 2 OCH 2 CF 2- HOCH 2 CH 2 CH 2 OCH 2 CF 2 CF 2- HOCH 2 CH 2 CH 2 OCH 2 CF 2- HOCH 2 CH 2 CH 2 OCH 2 CF 2- HOCH 2 CH 2 CH 2 OCH
- Examples of the group (X13) include the following groups. HOC (O) CF 2 CF 2 CF 2- HOC (O) CF 2 ⁇
- Examples of the group (X14) include the following groups. R 11 C (O) OCH 2 CF 2 CF 2 CF 2 — R 11 C (O) OCH 2 CF 2 —
- Examples of the group (X15) include the following groups. R 11 OC (O) CF 2 CF 2 CF 2 — R 11 OC (O) CF 2 —
- Examples of ⁇ in the group (X16) include the following groups.
- the substituent R 12 is a hydroxyl group, a halogen (where the halogen atom is a fluorine atom or a chlorine atom), an ester group, an alkoxy group, a hydrocarbon group, and an etheric oxygen atom inserted between the carbon atom and the carbon atom.
- Hydrocarbon group a hydrocarbon group having a nitrogen atom, a haloalkyl group (where a halogen atom is a fluorine atom or a chlorine atom), a haloalkoxy group (where a halogen atom is a fluorine atom or a chlorine atom) Or an aryl group, and p is an integer of 0 or more.
- the position of R 12 is not particularly limited, and when p is 2 or more, R 12 may be different, and the upper limit of p is a number as long as the aryl group can maintain aromaticity. is there. p is preferably 0 or 1.
- the group (X1) is preferably a group (X12) in which i is 2 from the viewpoint of excellent adhesion to the carbon protective film, and the following groups are particularly preferable from the viewpoint of easy production of the compound and excellent stability of the compound. preferable.
- i 2 from the viewpoint of excellent adhesion to the carbon protective film, and the following groups are particularly preferable from the viewpoint of easy production of the compound and excellent stability of the compound. preferable.
- (Y group) Y is an (m + n) -valent linking group that does not have an etheric oxygen atom at the terminal.
- the valence m + n of Y is an integer of 2 to 20, and is from 2 to 6 in view of excellent solubility of the compound (A) in a solvent, viscosity and lubricity, and ease of production of the compound (A). An integer is preferred.
- Y is an (m + n) -valent alkane group, an (m + n) -valent alkane group in which an etheric oxygen atom is inserted between carbon atoms and carbon atoms, an (m + n) -valent fluoroalkane group, or between carbon atoms and carbon atoms.
- (M + n) -valent fluoroalkane group having an etheric oxygen atom inserted therein, cyclotriphosphazene structure (P 3 N 3 ), etc. are applied, and the surface energy of the substrate is reduced by applying the compound (A).
- (m + n) -valent perfluoroalkane group, and (m + n) -valent perfluoroalkane group in which an etheric oxygen atom is inserted between carbon and carbon atoms. preferable.
- divalent Y examples include the following groups. -CF 2 CF 2- —CH 2 CH 2 —
- k is an integer of 0 to 5.
- tetravalent Y examples include the following groups.
- Group having Z Z does not have a hydroxyl group, a carboxy group, an ester group or an aryl group, and a haloalkyl group (wherein the halogen atom is a fluorine atom or a chlorine atom) or an etheric oxygen atom inserted between carbon atoms.
- a group having a haloalkyl group (wherein the halogen atom is a fluorine atom or a chlorine atom).
- the number n of the groups having Z is an integer of 0 to 10, from the viewpoint of excellent solubility of the compound (A) in a solvent, viscosity and lubricity, and from the viewpoint of easy production of the compound (A). 5 is preferred.
- Z is, for example, a haloalkyl group (wherein the halogen atom is a fluorine atom or a chlorine atom) or a haloalkyl group in which an etheric oxygen atom is inserted between a carbon atom and a carbon atom (wherein the halogen atom is a fluorine atom or A chlorine atom).
- Z examples include a group (Z1) represented by the following formula (Z1). -Q F (CH 2 ) j OR 21 (Z1)
- Q F is —CF 2 — or —CF 2 CF 2 CF 2 —
- R 21 represents a haloalkyl group (where a halogen atom is a fluorine atom or a chlorine atom) or a haloalkyl group in which an etheric oxygen atom is inserted between a carbon atom and a carbon atom (where a halogen atom is a fluorine atom or a chlorine atom)
- j is 1 or 2, and 1 is preferable from the viewpoint of easy production of the compound and excellent stability of the compound.
- R 21 in the group (Z1) examples include the following groups. —CH 2 CF 3 —CH (CF 3 ) 2 —CH 2 CF 2 CHF 2 —CH 2 CF 2 CF 2 CF 3 —CH 2 CF 2 CF 2 CF 2 CHF 2 —CH 2 CH 2 CF 2 CF 2 CF 2 CF 3 —CH 2 CH 2 CF 2 CF 2 CF 2 CF 3 —CH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 3 —CH 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 3 —CH 2 CCl 3 —CH 2 CH 2 Cl
- the polyether chain in the compound (A) is composed of (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 CF 2 O) units. Since the polyether chain consisting of only the (CF 2 CF 2 O) unit is insufficient in flexibility, the fluorinated polyether compound having the polyether chain is insufficient in lubricity. By introducing the (CF 2 CF 2 CF 2 CF 2 O) unit into the polyether chain, the polyether chain becomes relatively soft, and the fluorinated polyether compound having such a polyether chain has a lubricating property. Excellent.
- the polyether chain composed of (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units has sufficient flexibility of the polyether chain and uniform flexibility in the polyether chain. From the viewpoint of excellent properties, it is preferable to have a structure in which (OCF 2 CF 2 ) units and (OCF 2 CF 2 CF 2 CF 2 ) units are alternately arranged.
- a is an integer of 1 to 100, preferably 1 to 50, and particularly preferably 1 to 20 from the viewpoint of excellent solubility of the compound (A) in a solvent, viscosity and lubricity.
- b is an integer of 1 to 100, and is preferably 1 to 50 and particularly preferably 1 to 20 from the viewpoint of excellent solubility of the compound (A) in a solvent, viscosity and lubricity.
- b / (a + b) is preferably from 0.2 to 0.8, more preferably from 0.3 to 0.7 from the viewpoint that the flexibility of the polyether chain is sufficient and the lubricity of the compound (A) is excellent.
- 0.4 to 0.6 is preferable, and particularly preferable.
- the order of unit binding is not limited. That is, (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units may be randomly arranged, and (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2).
- CF 2 O) units may be alternately arranged, and one or more blocks composed of a plurality of (CF 2 CF 2 O) units and a plurality of (CF 2 CF 2 CF 2 CF 2 O) units.
- One or more blocks may be connected.
- (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units are alternately arranged [(CF 2 CF 2 O) a- (CF 2 CF 2 CF 2 O)
- Examples of b ] include the following polyether chains. —CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) e ⁇
- e is an integer of 1 to 99, preferably 1 to 50, and particularly preferably 1 to 20, from the viewpoint of excellent solubility of the compound (A) in a solvent, viscosity and lubricity.
- c is an integer of 1 to 100, and is preferably 1 to 50, particularly preferably 1 to 20, from the viewpoint of excellent solubility of the compound (A) in a solvent, viscosity, and lubricity.
- d is an integer of 1 to 100, and is preferably 1 to 50, particularly preferably 1 to 20, from the viewpoint of excellent solubility of the compound (A) in a solvent, viscosity, and lubricity.
- d / (c + d) is preferably from 0.2 to 0.8, more preferably from 0.3 to 0.7, from the viewpoint of sufficient flexibility of the polyether chain and excellent lubricity of the compound (A).
- 0.4 to 0.6 is preferable, and particularly preferable.
- (OCF 2 CF 2) units and may be a (OCF 2 CF 2 CF 2 CF 2) units are randomly arranged, (OCF 2 CF 2) units and (OCF 2 CF 2 CF 2 CF 2)
- the units may be alternately arranged, and one or more blocks composed of a plurality of (OCF 2 CF 2 ) units and one or more blocks composed of a plurality of (OCF 2 CF 2 CF 2 CF 2 ) units; May be connected.
- the flexibility of the polyether chain is sufficient and the uniformity of flexibility in the chain is excellent ( It is preferable to have a structure in which OCF 2 CF 2 ) units and (OCF 2 CF 2 CF 2 CF 2 ) units are alternately arranged, and have 50% or more of the alternately arranged structure portions in the polyether chain More preferably, it is more preferably 80% or more, and particularly preferably 90% or more.
- the compound (A) preferably has no —OCF 2 O— structure from the following points.
- ⁇ -OCF fluorine-containing polyether compound having a 2 O- structure compared with a fluorine-containing polyether compound having no -OCF 2 O- structure, chemical stability is poor.
- the polyether chain has a (CF 2 O) unit, the polyether chain becomes too flexible and enters a random coil state. For this reason, when it is applied to a substrate, it becomes a lump and rises, making it difficult to thin the coating.
- the number average molecular weight of the compound (A) is preferably 500 to 50,000, more preferably 500 to 10,000, and particularly preferably 1,000 to 5,000. If the number average molecular weight of a compound (A) is more than the said lower limit, it is excellent in the solubility to a solvent, a viscosity, and lubricity. If the number average molecular weight of the compound (A) is not more than the above upper limit value, it will be difficult to volatilize during use when coated on a magnetic disk.
- Fluorine-containing polyether compound introduced with X at one end of the polyether chain, and optionally fluorine-containing polyether compound introduced with Z at one end of the polyether chain, (m + n) A method of reacting with a compound having —SO 2 CH 3 group or the like.
- methods (1-1) to (1-3) will be described as examples of the method (1), and methods (2-1) to (2-2) will be described as examples of the method (2).
- Y F is an (m + n) -valent perfluoroalkane group that does not have an etheric oxygen atom at the terminal, or an (m + n) -valent perfluoroalkane group in which an etheric oxygen atom is inserted between carbon and carbon atoms.
- HOCH 2 CF 2 CF 2 CF 2 — in the compound (A1) is a group (X11)
- HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 — in the compound (A2) is a group (X12)
- R 11 OC (O) CF 2 CF 2 CF 2 — in the compound (A5) is a group (X15).
- the compound (1) represented by the following formula (1) is reduced with a reducing agent (such as sodium borohydride) to obtain the compound (2) represented by the following formula (2).
- a reducing agent such as sodium borohydride
- CF 2 CFOCF 2 CF 2 CF 2 C (O) OCH 3
- CF 2 CFOCF 2 CF 2 CF 2 CH 2 OH
- Y 1 is an (m + n) -valent alkane group having no ether oxygen atom at the end and CH 2 at the end, and an ether oxygen atom inserted between the carbon atom and the carbon atom (m + n).
- a compound (6) represented by the following formula (6) is obtained by esterification reaction of the compound (4) and the compound (5) represented by the following formula (5).
- R f is a perfluoroalkyl group or a perfluoroalkyl group having an etheric oxygen atom inserted between carbon atoms.
- acid fluoride of the compound (5) acid chloride, acid bromide, acid anhydride or the like may be used.
- the compound (7) represented by the following formula (7) is obtained by substituting the fluorine atom for the hydrogen atom of the compound (6) using fluorine gas.
- the fluorination can be performed, for example, according to the method described in International Publication No. 2000/56694. ⁇ R f C (O) O— (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) e + 1 ⁇ m —Y F (7)
- Compound (A5) is obtained by reacting compound (7) with compound (8) represented by the following formula (8).
- R 11 OH (8) ⁇ R 11 OC (O) CF 2 CF 2 CF 2 —O—CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) e ⁇ m —Y F (A5)
- Compound (A1) is obtained by reducing compound (A5) with a reducing agent (such as sodium borohydride). ⁇ HOCH 2 CF 2 CF 2 CF 2 —O—CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) e ⁇ m —Y F (A1)
- a reducing agent such as sodium borohydride
- Compound (A2) is obtained by reacting compound (A1) with compound (9) represented by the following formula (9).
- Compound (A1) is obtained in the same manner as in Method (1-1). ⁇ HOCH 2 CF 2 CF 2 CF 2 —O—CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) e ⁇ m + n —Y F (A1)
- the compound (A1) is reacted with metallic sodium or a basic compound (sodium hydride, potassium tert-butoxide), and then further reacted with the compound (11).
- the obtained crude product is purified with a silica gel column by the method described in Examples of JP-A-2009-197210 to obtain compound (A11).
- Compound (A1) is obtained in the same manner as in Method (1-1). ⁇ HOCH 2 CF 2 CF 2 CF 2 —O—CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 O) e ⁇ m —Y F (A1)
- compound (A6) Get After reacting compound (A1) with metallic sodium or a basic compound (sodium hydride, potassium tert-butoxide), further reacting with compound (12) represented by the following formula (12), compound (A6) Get.
- A is a hydroxyl group, an iodine atom or a bromine atom. In the case of a hydroxyl group, it can be used after reacting with mesyl chloride as in the method (1-2).
- Y 2 is an (m + n) -valent alkane group having no etheric oxygen atom at the end and CH 2 at the end, and (m + n) -valent with an etheric oxygen atom inserted between the carbon atom and the carbon atom.
- ⁇ -Q F (CH 2 ) j O ⁇ m -Y 2- ⁇ O (CH 2 ) j Q F- ⁇ n corresponds to Y, ⁇ Q 12 O (CH 2 ) j Q F -is a group (X16), -Q F (CH 2 ) j OR 21 is a group (Z1).
- a compound (13) represented by the following formula (13) and a compound (14) represented by the following formula (14) are prepared.
- the production method of the compound (13) and the compound (14) will be described in the method (3) described later.
- ⁇ Q F (CH 2 ) j O ⁇ m1 ⁇ P 3 N 3 ⁇ ⁇ O (CH 2 ) j Q F ⁇ n1 corresponds to Y, ⁇ Q 12 O (CH 2 ) j Q F -is a group (X16), -Q F (CH 2 ) j OR 21 is a group (Z1).
- the compound (16) is reacted with metallic sodium or a basic compound (sodium hydride, potassium tert-butoxide), and then the mixture of the compound (20) is further reacted to obtain a mixture of the compound (A63).
- Method (3-1) is a production example of compound (13) in which (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units are alternately arranged.
- Compound (13) in which (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units are alternately arranged is used in the production of compound (A1) by method (1-1). Further, it can be produced by using the compound (3-1) represented by the following formula (3-1) as the compound (3). HO—CH 2 CH 2 —OH (3-1)
- Method (3-2) is a production example of compound (13) in which (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 CF 2 O) units are randomly arranged.
- a compound (21) represented by the following formula (21) is prepared.
- a1 is an integer of 1 to 100
- b1 is an integer of 1 to 100.
- Examples of commercially available products of compound (21) include polyserine (registered trademark) series (DC-1100, DC-1800E, 60DC-1800, DC-3000E) manufactured by NOF Corporation.
- a compound (22) represented by the following formula (22) is obtained by an esterification reaction of the compound (21) and the compound (5).
- R f C (O) F (5) R f C (O) O — [(CH 2 CH 2 O) a1 — (CH 2 CH 2 CH 2 CH 2 O) b 1 ] —C (O) R f (22)
- a compound (23) represented by the following formula (23) is obtained by substituting a hydrogen atom of the compound (22) with a fluorine atom using fluorine gas.
- Compound (8) is allowed to act on compound (23) to obtain a mixture of compounds (24i) to (24iii) represented by the following formulae.
- R 11 OH (8) R 11 OC (O) CF 2 CF 2 CF 2 —O — [(CF 2 CF 2 O) a1 — (CF 2 CF 2 CF 2 O) b1-2 ] —CF 2 CF 2 CF 2 C (O ) OR 11 ...
- the mixture of compounds (24i) to (24iii) is reduced with a reducing agent (such as sodium borohydride) to obtain a mixture of compounds (13ai) to (13aiii) represented by the following formulae.
- a reducing agent such as sodium borohydride
- a compound (25) represented by the following formula (25) and a compound (26) represented by the following formula (26) are prepared.
- a2 is an integer from 1 to 51
- b2 is an integer from 1 to 51.
- a polyethylene glycol PEG # 200T, PEG # 200, PEG # 300, PEG # 400, PEG # 600, PEG # 1000, PEG # 1540, PEG # 2000
- Examples of commercially available products of the compound (26) include the Uniol (registered trademark) series (PB-500, PB-700, PB-1000, PB-2000, PB-4800) manufactured by NOF Corporation.
- the compound (26) is reacted with sodium metal or a basic compound (sodium hydride, potassium tert-butoxide) and then further reacted with the compound (27) to give a compound (29i) represented by the following formula (29i) Get.
- the compound (25) is reacted with metallic sodium or a basic compound (sodium hydride, potassium tert-butoxide) and then further reacted with the compound (28) to obtain a compound represented by the following formula (29ii) ( 29ii).
- a compound (30i) represented by the following formula (30i) or a compound (30ii) represented by the following formula (30ii) is obtained by an esterification reaction of the compound (29i) or the compound (29ii) and the compound (5).
- R f C (O) F (5) R f C (O) O— (CH 2 CH 2 O) a 2 — (CH 2 CH 2 CH 2 CH 2 O) b 2 — (CH 2 CH 2 O) a 2 —C (O) R f (30i ) R f C (O) O- ( CH 2 CH 2 CH 2 CH 2 O) b2 - (CH 2 CH 2 O) a2 - (CH 2 CH 2 CH 2 CH 2 O) b2 -C (O) R f ⁇ .. (30ii)
- a compound (31i) represented by the following formula (31i) or a compound represented by the following formula (31ii) by substituting the hydrogen atom of the compound (30i) or the compound (30ii) with a fluorine atom using fluorine gas ( 31ii) is obtained.
- the compound (8i) is allowed to act on the compound (31i) or the compound (31ii) to obtain the compound (32i) represented by the following formula (32i) or the compound (32ii) represented by the following formula (32ii).
- R 11 OH (8)
- Compound (32i) or compound (32ii) is reduced with a reducing agent (such as sodium borohydride) and then compound (13bi) represented by the following formula (13bi) or compound (13bii) represented by the following formula (13bii) Get.
- a reducing agent such as sodium borohydride
- the fluorinated polyether compound (A) having a polyether chain composed of (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 CF 2 O) units is excellent in lubricity.
- the fluorine-containing polyether compound (A) is required to have a -OCF 2 O-structure, compared with a fluorine-containing polyether compound having -OCF 2 O-structure, excellent chemical stability. Further, since the linearity is higher than that of the fluorine-containing polyether compound having the —OCF 2 O— structure, and a random coil state is not obtained, it is possible to cope with a thin coating film.
- X in the formula (A) is a HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 — group or a HOCH 2 CH (OH) CH 2 OCH 2 CF 2 — group, Excellent adhesion.
- the second aspect of the fluorine-containing polyether compound of the present invention is a fluorine-containing polyether compound (B) represented by the following formula (B) (hereinafter also referred to as compound (B)).
- X group is a group having a hydroxyl group, a carboxy group, an ester group or an aryl group. Examples and preferred embodiments of X are the same as those of the fluorine-containing polyether compound (A), and details thereof are omitted. Hereinafter, the details of the same reference numerals as those in the fluorine-containing polyether compound (A) are also omitted.
- W group W represents a hydroxyl group, a carboxy group, an ester group, an aryl group, a haloalkyl group (wherein the halogen atom is a fluorine atom or a chlorine atom), or a haloalkyl group in which an etheric oxygen atom is inserted between carbon atoms. (However, the halogen atom is a fluorine atom or a chlorine atom.)
- W examples include a group (W1) represented by the following formula (W1) or a group (W2) represented by the following formula (W2).
- R 2 represents a haloalkyl group (where a halogen atom is a fluorine atom or a chlorine atom) or a haloalkyl group in which an etheric oxygen atom is inserted between a carbon atom and a carbon atom (where a halogen atom is a fluorine atom or a chlorine atom) Is.) -Q 1- (X 1 ) i (W1) -R 2 (W2)
- Examples of the group (W1) include a group (W11) represented by the following formula (W11), a group (W12) represented by the following formula (W12), and a group (W13) represented by the following formula (W13).
- Examples of the group (W2) include a group (W21) represented by the following formula (W21). -Q F (CH 2 ) j OR 21 (W21)
- W is preferably a group having i of 2 (W12) from the viewpoint of excellent adhesion to the carbon protective film, and the following groups are particularly preferable from the viewpoint of easy production of the compound and excellent stability of the compound. —CF 2 CF 2 CF 2 CH 2 OCH 2 CH (OH) CH 2 OH —CF 2 CH 2 OCH 2 CH (OH) CH 2 OH
- the polyether chain in the compound (B) is composed of (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 CF 2 O) units. Since the polyether chain consisting of only the (CF 2 CF 2 O) unit is insufficient in flexibility, the fluorine-containing polyether compound having the chain is insufficient in lubricity. By introducing the (CF 2 CF 2 CF 2 CF 2 O) unit into the chain, the polyether chain becomes relatively soft, and the fluorinated polyether compound having the chain is excellent in lubricity.
- g is an integer of 1 to 200, preferably 1 to 100, and particularly preferably 1 to 40, from the viewpoint of excellent solubility of the compound (B) in a solvent, viscosity, and lubricity.
- h is an integer of 1 to 200, preferably 1 to 100, and particularly preferably 1 to 40, from the viewpoint of excellent solubility of the compound (B) in a solvent, viscosity, and lubricity.
- h / (g + h) is preferably 0.2 to 0.8, more preferably 0.3 to 0.7, from the viewpoint that the polyether chain has sufficient flexibility and is excellent in the lubricity of the compound (B).
- 0.4 to 0.6 is preferable, and particularly preferable.
- the order of O) units is not limited. That is, (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units may be randomly arranged, and (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2). CF 2 O) units may be alternately arranged, and one or more blocks composed of a plurality of (CF 2 CF 2 O) units and a plurality of (CF 2 CF 2 CF 2 CF 2 O) units.
- One or more blocks may be connected.
- the chain preferably has a structure in which (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units are alternately arranged in the chain, and the alternately arranged structural parts in the polyether chain Is more preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more.
- the compound (B) preferably has no —OCF 2 O— structure for the same reason as the fluorine-containing polyether compound (A).
- the number average molecular weight of the compound (B) is preferably 500 to 50,000, more preferably 500 to 10,000, and particularly preferably 1,000 to 5,000 for the same reason as the fluorine-containing polyether compound (A). .
- the fluorine-containing polyether compound (B) can be produced in the same manner as the fluorine-containing polyether compound (A). It can also be obtained as an intermediate obtained in the production process of the fluorine-containing polyether compound (A).
- the compound (B1) represented by the following formula (B1) is obtained by the method (3-1) described above.
- (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 O) units are alternately arranged except for a part.
- the compound (B2) represented by the following formula (B2) is obtained from the compound (B1) by the last step of the method (1-1) described above.
- HOCH 2 CH (OH) CH 2 O (CH 2 ) j Q F —O — [(CF 2 CF 2 O) g — (CF 2 CF 2 CF 2 CF 2 O) h ] —Q F (CH 2 ) j OCH 2 CH (OH) CH 2 OH (B2)
- the compounds (24i) to (24iii) and the compounds (13ai) to (13aiii) obtained by the method (3-2) described above also correspond to the fluorinated polyether compound (B).
- the compound (32i), the compound (32ii), the compound (13bi), and the compound (13bii) obtained by the above method (3-3) also correspond to the fluorine-containing polyether compound (B).
- the compounds (15) and (16) obtained by the above method (2-1) also correspond to the fluorine-containing polyether compound (B).
- the manufacturing method of a fluorine-containing polyether compound (B) is not limited to these.
- the fluorine-containing polyether compound (B) described above since the polyether chain is composed of (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 CF 2 O) units, (CF 2 CF Compared to a polyether chain composed of only 2 O) units, it is excellent in flexibility. Therefore, the fluorine-containing polyether compound (B) having a polyether chain composed of (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 CF 2 O) units is excellent in lubricity.
- the fluorine-containing polyether compound (B) is required to have a -OCF 2 O-structure, compared with a fluorine-containing polyether compound having -OCF 2 O-structure, excellent chemical stability. Further, since the linearity is higher than that of the fluorine-containing polyether compound having the —OCF 2 O— structure, and a random coil state is not obtained, it is possible to cope with a thin coating film. Further, when X in the formula (B) is a HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 — group or a HOCH 2 CH (OH) CH 2 OCH 2 CF 2 — group, Excellent adhesion.
- the fluorine-containing polyether compound of the present invention is useful as a surface modifier or a surfactant.
- the surface modifier include a lubricant.
- fluorine-containing polyether compound of the present invention include wire coating materials, ink repellents (for example, for printing, for printing equipment such as inkjets), and semiconductor element adhesives (for example, LOC (lead-on-chip) tapes) Adhesives), protective coatings for semiconductors (for example, moisture-proof coating agents, anti-cracking agents for soldering), additives for thin films used in the optical field (for example, pellicle films), lubricants for anti-reflection coatings for displays, reflections for resists Examples thereof include a prevention film.
- ink repellents for example, for printing, for printing equipment such as inkjets
- semiconductor element adhesives for example, LOC (lead-on-chip) tapes
- Adhesives Adhesives
- protective coatings for semiconductors for example, moisture-proof coating agents, anti-cracking agents for soldering
- additives for thin films used in the optical field for example, pellicle films
- the fluorinated polyether compound of the present invention is suitably used for the purpose of forming a film (surface layer) containing the fluorinated polyether compound of the present invention on a substrate. Since the surface layer contains the fluorine-containing polyether compound of the present invention having a hydroxyl group, a carboxy group, an ester group or an aryl group at the molecular terminal, high lubricity is maintained. Therefore, functions such as lubricity can be imparted by providing the surface layer on the substrate. Further, the surface layer has high adhesion to the substrate and is excellent in durability.
- the surface layer is transparent, has a low refractive index, and is excellent in heat resistance or chemical resistance.
- the shape and material of the base material are not particularly limited, and those according to the purpose of the base material provided with the surface layer can be used as appropriate.
- Examples of the use of the substrate provided with the surface layer include various films such as magnetic disks, optical fibers, mirrors, solar cells, optical disks, touch panels, photosensitive and fixing drums, film capacitors, and antireflection films for glass windows. .
- the thickness of the surface layer is appropriately set according to the application.
- the thickness of the surface layer is determined by, for example, obtaining an interference pattern of reflected X-rays by an X-ray reflectivity method using an X-ray diffractometer for thin film analysis (manufactured by RIGAKU Co., Ltd., ATX-G). It can be calculated from
- a liquid composition may be added to the fluorine-containing polyether compound of the present invention to add a liquid medium.
- a liquid medium is added to the fluorinated polyether compound of the present invention to form a liquid composition. It is preferable to use it as a product.
- the lubricant of the present invention contains the fluorine-containing polyether compound of the present invention.
- the lubricant of the present invention may contain one kind of fluorine-containing polyether compound (A) alone, and one or more of X, Y, Z, m, n, and ad in the formula (A) May contain two or more kinds of fluorine-containing polyether compounds (A) different from each other.
- one kind of fluorine-containing polyether compound (B) may be contained alone, and one or more of X, W, g, and h in the formula (B) are different from each other in the fluorine-containing polyether compound (B). Two or more kinds may be included.
- the fluorine-containing polyether compound (A) and the fluorine-containing polyether compound (B) may be included.
- the lubricant of the present invention may be composed only of the fluorine-containing polyether compound of the present invention, or may further contain other components.
- the content of the fluorine-containing polyether compound of the present invention in the lubricant of the present invention is preferably 90 to 100% by mass, particularly preferably 100% by mass, based on the total mass of the lubricant. That is, it is particularly preferable that the lubricant of the present invention comprises only the fluorine-containing polyether compound of the present invention.
- any compound that can be used as a lubricant and does not fall under the fluorine-containing polyether compound of the present invention can be used.
- fluorine-containing polyether compounds other than the fluorine-containing polyether compound of the present invention Silane-based, epoxy-based, titanium-based, aluminum-based coupling agents, and the like.
- the adhesion between the substrate and the fluorine-containing polyether compound of the present invention can be improved by using the coupling agent.
- a use for a magnetic disk particularly a use for applying lubricity on a diamond-like carbon protective film (DLC film) of the magnetic disk is preferable.
- the magnetic disk for example, a magnetic disk having a base layer, a magnetic recording layer, and a diamond-like carbon protective film (DLC film) in this order on a NiP-plated substrate (aluminum, glass, etc.) can be mentioned.
- the thickness of the DLC film is preferably 5 nm or less.
- the average surface roughness (Ra) of the DLC film is preferably 2 nm or less.
- the thickness is preferably 0.1 to 2 nm, particularly preferably 0.5 to 1 nm. If the thickness of the surface layer is equal to or more than the lower limit value, the lubricating effect by the surface layer can be sufficiently obtained. If the thickness of the surface layer is not more than the above upper limit value, it can contribute to high density recording of the magnetic disk. According to the fluorine-containing polyether compound of the present invention, a surface layer exhibiting sufficient lubricity can be formed even if it is thinned. Therefore, the thinner the surface layer, the higher the usefulness of the present invention.
- the liquid composition of the present invention contains the fluorinated polyether compound of the present invention and a liquid medium.
- the liquid composition of the present invention may be a solution, a suspension, or an emulsion, and is preferably a solution.
- the concentration of the fluorine-containing polyether compound of the present invention in the liquid composition can be appropriately adjusted according to the use, and is preferably 0.005 to 50% by mass with respect to the total mass of the liquid composition, 0.005 Is more preferably 5% by mass, and particularly preferably 0.01-1% by mass. When the concentration of the fluorinated polyether compound of the present invention is within the above range, a uniform surface layer can be formed.
- the liquid medium is not particularly limited as long as it can dissolve or disperse the fluorine-containing polyether compound of the present invention, and an organic solvent is preferable.
- the organic solvent may be a fluorinated organic solvent, a non-fluorinated organic solvent, or may contain both of these solvents.
- fluorine-based organic solvent examples include fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, fluoroalkylamines, and fluoroalcohols.
- fluoroalkane a compound having 4 to 8 carbon atoms is preferable.
- commercially available products include C 6 F 13 H (Asahi Glass Co., Ltd., AC-2000), C 6 F 13 C 2 H 5 (Asahi Glass Co., Ltd., AC-6000), C 2 F 5 CHFCHFCF 3 (Du Pont Corp., Vertrel (registered trademark) XF) and the like.
- fluoroaromatic compound examples include hexafluorobenzene, trifluoromethylbenzene, perfluorotoluene, bis (trifluoromethyl) benzene, and the like.
- fluoroalkyl ether a compound having 4 to 12 carbon atoms is preferable.
- fluoroalkyl ether hydrofluoroalkyl ether is preferable. Examples of commercially available products include CF 3 CH 2 OCF 2 CF 2 H (Asahi Glass Co., AE-3000), C 4 F 9 OCH 3 (3M, Novec (registered trademark) -7100), C 4 F 9 OC.
- fluoroalkylamine perfluoroalkylamine is preferable, and examples thereof include perfluorotripropylamine and perfluorotributylamine.
- fluoroalcohol examples include 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol and the like.
- fluorine-based organic solvent fluoroalkanes, fluoroaromatic compounds, and fluoroalkyl ethers are preferable from the viewpoint of solubility of the fluorine-containing polyether compound.
- hydrofluoroalkyl ether is particularly preferable because it has a low ozone depletion coefficient.
- non-fluorine-based organic solvent a compound consisting only of a hydrogen atom and a carbon atom and a compound consisting only of a hydrogen atom, a carbon atom and an oxygen atom are preferable, a hydrocarbon-based organic solvent, an alcohol-based organic solvent, a ketone-based organic solvent, Examples include ether organic solvents and ester organic solvents.
- a hydrocarbon organic solvent hexane, heptane, cyclohexane and the like are preferable.
- alcohol organic solvent methanol, ethanol, propanol, isopropanol and the like are preferable.
- ketone organic solvent acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferable.
- ether organic solvent diethyl ether, tetrahydrofuran, tetraethylene glycol dimethyl ether and the like are preferable.
- ester organic solvent ethyl acetate, butyl acetate and the like are preferable.
- non-fluorine organic solvent a ketone organic solvent is particularly preferable from the viewpoint of the solubility of the fluorine-containing polyether compound.
- the liquid medium is at least one selected from the group consisting of fluoroalkanes, fluoroaromatic compounds, fluoroalkyl ethers, compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms and oxygen atoms.
- Some organic solvents are preferred.
- a fluorine-based organic solvent selected from fluoroalkanes, fluoroaromatic compounds and fluoroalkyl ethers is preferred.
- the liquid medium is at least selected from the group consisting of fluoroalkanes that are fluorine-based organic solvents, fluoroaromatic compounds, fluoroalkyl ethers, and compounds that consist of only hydrogen atoms, carbon atoms, and oxygen atoms that are non-fluorine-based organic solvents. It is preferable in terms of increasing the solubility of the fluorinated polyether compound that a total of 90% by mass of one organic solvent is contained in the total liquid medium.
- the liquid composition may further contain other components other than the fluorinated polyether compound of the present invention and the liquid medium as needed, as long as the effects of the present invention are not impaired.
- other components include radical scavengers (for example, X-1p manufactured by Dow Chemicals).
- the liquid composition may not achieve the desired performance, it is preferable that the liquid composition does not contain metal ions, anions, moisture, low-molecular polar compounds, and the like.
- Metal ions Na, K, Ca, Al, etc.
- Anions F, Cl, NO 2 , NO 3 , PO 4 , SO 4 , C 2 O 4 etc.
- the water content in the liquid composition is preferably 2,000 ppm or less.
- Low molecular polar compounds (alcohols; plasticizers eluted from the resin, etc.) may reduce the adhesion between the substrate and the surface layer.
- Method of using fluorine-containing polyether compound As a method for using the fluorinated polyether compound or the liquid composition, a known method can be applied depending on the purpose. For example, when the fluorine-containing polyether compound of the present invention is used as a lubricant, the fluorine-containing polyether compound of the present invention is applied on a substrate or a liquid containing the fluorine-containing polyether compound of the present invention. A film (surface layer) containing the fluorine-containing polyether compound of the present invention is formed by applying the composition onto a substrate and drying (that is, removing the liquid medium from the liquid composition). It is preferable to express the function.
- the base material to which the fluorine-containing polyether compound of the present invention or the liquid composition containing the same is applied is not particularly limited, and examples thereof include those similar to those mentioned above as the base material on which the surface layer is provided.
- a magnetic disk is preferable from the viewpoint of the usefulness of the present invention.
- Examples of the coating method of the fluorine-containing polyether compound and the liquid composition containing the same include, for example, a roll coating method, a casting method, a dip coating method, a spin coating method, a water casting method, a die coating method, a Langmuir / Projet method, and vacuum deposition.
- Examples of the method include spin coating, dip coating, and vacuum deposition.
- examples of the drying method include natural drying, vacuum drying, centrifugal drying, and heat drying.
- the fluorinated polyether compound of the present invention is firmly adhered to the substrate (for example, on the carbon protective film of the magnetic disk).
- the contact treatment may be performed.
- the adhesion treatment include heat treatment, infrared irradiation treatment, ultraviolet irradiation treatment, and plasma treatment. Heat treatment or ultraviolet irradiation treatment is preferable, and heat treatment is particularly preferable.
- the drying process may also serve as an adhesion process.
- the substrate after the adhesion treatment may be washed with a fluorinated organic solvent for the purpose of removing deposits and excess fluorine-containing polyether compound.
- the article of the present invention has a film containing the fluorinated polyether compound of the present invention on a substrate.
- coats the liquid composition of this invention is not specifically limited, For example, the thing similar to what was mentioned above as a base material which provides a surface layer is mentioned.
- As the substrate a magnetic disk is preferable from the viewpoint of the usefulness of the present invention.
- As a method of providing the film on the substrate a known method can be used as a method of forming a film made of a fluorine-containing polyether compound.
- the film can be formed by a method of forming the surface layer by applying the liquid composition of the present invention described above onto a substrate.
- Examples 1, 2, and 5 to 8 are examples, and examples 3 and 4 are comparative examples.
- the evaluation method in each example is shown below.
- GPC analysis The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography (hereinafter also referred to as GPC). In addition, Mw shows a mass average molecular weight. Measurement by GPC was performed under the following conditions in accordance with the method described in JP-A No. 2001-208736.
- Analytical column Two PLgel MIXED-E columns (manufactured by Polymer Laboratories) connected in series.
- Standard sample for molecular weight measurement 4 types of perfluoropolyethers with Mw / Mn of less than 1.1 and Mn of 2,000 to 10,000, and perfluoro with Mw / Mn of 1.1 or more and Mn of 1,300 1 type of polyether.
- Mobile phase flow rate 1.0 mL / min.
- Column temperature 37 ° C.
- Detector Evaporative light scattering detector.
- F / Si The coverage of the surface layer provided on the substrate (silicon wafer) is determined by the following criteria by F / Si measured under the following measurement conditions by X-ray photoelectron spectroscopy (XPS). evaluated. ⁇ (Good): F / Si is 0.8 to 1.0. X (defect): F / Si is less than 0.8 or more than 1.0.
- XPS X-ray photoelelectrons emitted by the photoelectric effect
- the bond energy Eb is a value that depends on the type of atom in which photoelectrons have been captured in the sample, the electron orbit, and the chemical bond state.
- the energy h ⁇ and work function W of the incident X-ray are known. Therefore, if the kinetic energy Ek is measured, the bond energy Eb can be obtained, and the type, electron orbit, and chemical bond state of atoms in the sample can be known.
- Incident X-rays penetrate to a depth of about several ⁇ m. However, electrons emitted from atoms in deep locations lose energy due to inelastic scattering with electrons bound to other atoms in the sample, and are not emitted from the sample.
- XPS is a method for measuring the type and amount of atoms present on the outermost surface of a sample and the chemical bonding state with high sensitivity, and can detect an extremely thin film coated on a substrate with high sensitivity. This is an effective method for evaluating the coverage of the material.
- the ratio of F atom concentration and Si atom concentration calculated from the F1s peak intensity and Si2p peak intensity obtained by XPS measurement is considered to have a positive correlation with the coverage of the surface layer provided on the substrate. be able to.
- PHI Quantera SXM manufactured by ULVAC-PHI was used as an XPS apparatus.
- AlK ⁇ ray (1486.6 eV) focused to a diameter of about 50 ⁇ m as an X-ray source measurement was performed at an irradiation X-ray intensity of 12.4 W, a detector pass energy of 224 eV, and a photoelectron extraction angle of 45 °.
- Irradiated X-rays were fixed and measured without scanning, and the sample outermost surface was measured, and the sample was not etched. Note that an electron beam attached to the apparatus and an Ar + neutralization gun were used for charge correction accompanying photoelectron emission from the sample.
- the F1s peak intensity was calculated using the binding energy 682 to 691 eV, and the Si2p peak intensity using the integrated intensity of the peak with the background removed in the energy range of the binding energy 96 to 107 eV. Furthermore, F atom concentration and Si atom concentration were calculated using the relative sensitivity coefficient of each element unique to the apparatus.
- Example 1 (Example 1-1) Into a 300 mL three-necked round bottom flask, 14.1 g of sodium borohydride powder was taken, and 350 g of AK-225 (Asahi Glass Co., Ltd.) was added. Stir while cooling in an ice bath, and slowly add from a dropping funnel a mixture of 100 g of compound (1), 15.8 g of methanol, and 22 g of AK-225 under a nitrogen atmosphere so that the internal temperature does not exceed 10 ° C. It was dripped. After the entire amount was dropped, a solution in which 10 g of methanol and 10 g of AK-225 were mixed was further dropped.
- AK-225 Asahi Glass Co., Ltd.
- Example 1-2 To a 500 mL eggplant flask connected with a reflux condenser, 100 g of compound (2), 11.0 g of compound (3-1), and 25.2 g of potassium carbonate powder were added. After stirring at 75 ° C. for 1 hour in a nitrogen atmosphere, the temperature was raised to 120 ° C., and 200 g of compound (2) was added dropwise while controlling the internal temperature to be 130 ° C. or lower. After the entire amount was dropped, the mixture was further stirred at 120 ° C. for 1 hour. It was confirmed by NMR that the vinyl ether group of compound (2) had completely disappeared. An aqueous hydrochloric acid solution was added to treat excess potassium carbonate, and water and AK-225 were added to carry out a liquid separation treatment.
- the organic phase was recovered and concentrated by an evaporator to obtain 310 g of the compound (4-1) represented by the following formula (4-1).
- the compound (4-1) was diluted with 110 g of AK-225, developed by silica gel column chromatography (developing solvent: AK-225, ethyl acetate), fractionated, impurities removed, and molecular weight purified. Of 150 g was obtained.
- AK-225 developed by silica gel column chromatography (developing solvent: AK-225, ethyl acetate), fractionated, impurities removed, and molecular weight purified. Of 150 g was obtained.
- HO—CH 2 CH 2 —OH (3-1) HO— (CH 2 CF 2 CF 2 CF 2 OCHFCF 2 O) 3 —CH 2 CH 2 — (OCF 2 CHFOCF 2 CF 2 CF 2 CH 2 ) 3 —OH (4-1)
- Example 1-3 Into a 300 mL eggplant flask connected to a reflux condenser, 100 g of compound (4-1) and 9.0 g of sodium fluoride powder were introduced, and the compound (5-1) represented by the following formula (5-1) 40 g was added. The mixture was stirred at 50 ° C. for 13 hours under a nitrogen atmosphere, and then stirred at 70 ° C. for 3 hours. After removing the sodium fluoride powder with a pressure filter, excess compound (5-1) and AK-225 were distilled off under reduced pressure, and the compound (6-1) represented by the following formula (6-1) was removed. 130 g (97% yield) were obtained.
- Example 1-4 An autoclave (made of nickel, internal volume 1 L) was prepared, and a cooler maintained at 0 ° C., a packed bed of NaF pellets, and a cooler maintained at ⁇ 10 ° C. were installed in series at the gas outlet of the autoclave. In addition, a liquid return line for returning the liquid aggregated from the cooler maintained at ⁇ 10 ° C. to the autoclave was installed. 750 g of R-113 (CF 2 ClCFCl 2 ) was added to the autoclave and stirred while maintaining at 25 ° C. After blowing nitrogen gas into the autoclave at 25 ° C.
- fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was added at 25 ° C. and a flow rate of 3.2 L / hour for 1 hour. Infused.
- 20% fluorine gas diluted to 20% by volume with nitrogen gas
- a solution of 130 g of compound (6-1) dissolved in 448 g of R-113 was injected into the autoclave over 20 hours while blowing 20% fluorine gas at the same flow rate.
- the internal pressure of the autoclave was increased to 0.15 MPa (gauge pressure) while blowing 20% fluorine gas at the same flow rate.
- Example 1-5 In a 500 mL round bottom eggplant flask made of tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer (PFA), 145 g of compound (7-1) was placed. The mixture was stirred while being cooled in an ice bath, and 35 g of methanol was slowly dropped from the dropping funnel under a nitrogen atmosphere. The mixture was stirred for 12 hours while bubbling with nitrogen. The reaction mixture was concentrated with an evaporator to obtain 108 g (yield 100%) of the compound (A5-1) represented by the following formula (A5-1).
- PFA tetrafluoroethylene-perfluoro (alkoxy vinyl ether) copolymer
- Example 1-6 In a 300 mL three-necked round bottom flask, 200 g of ethanol, 2.1 g of lithium chloride, and 100 g of compound (A5-1) were introduced and stirred while cooling in an ice bath. Under a nitrogen atmosphere, sodium borohydride powder A solution prepared by dissolving 9.5 g of the above in 200 g of ethanol was added dropwise. After the entire amount was dropped, the ice bath was removed, and stirring was continued for 12 hours while slowly warming to room temperature. Thereafter, the mixture was cooled again in an ice bath, and an aqueous hydrochloric acid solution was added dropwise until the liquid became acidic.
- Example 2 Into a 300 mL three-necked round bottom flask is taken 50 g of tert-butyl alcohol, 5.6 g of potassium tert-butoxide, and 100 g of compound (A1-1) (as a crude product) before purification. Stirring while heating, 7.4 g of glycidol (compound (9)) was added dropwise under a nitrogen atmosphere. After the entire amount was dropped, stirring was continued for 5 hours. Then, it cooled with the ice bath and hydrochloric acid aqueous solution was dripped until the liquid property became acidic. After completion of the reaction, the organic phase was recovered by washing once with water and once with saturated saline.
- the collected liquid was concentrated with an evaporator.
- the collected concentrated liquid was distilled under reduced pressure and purified in the same manner as in Example 1 to obtain 100 g (yield 93%) of the compound (A2-1) represented by the following formula (A2-1).
- the number average molecular weight of the compound (A2-1) was 2,200, and the molecular weight distribution was 1.05.
- An article was obtained in the same manner as in Example 1 except that the compound (A2-1) was used.
- Example 3 A compound (C-1) represented by the following formula (C-1) (manufactured by Solvay, Fomblin (registered trademark) Z DOL4000, number average molecular weight 4,000) was prepared. An article was obtained in the same manner as in Example 1 except that the compound (C-1) was used. HO— (CF 2 O) s (CF 2 CF 2 O) t —H (C-1)
- Example 4 A 300 mL three-necked round bottom flask was charged with 50 g of tert-butyl alcohol, 2.8 g of potassium tert-butoxide and 100 g of compound (C-1), stirred while heating to 80 ° C., and under nitrogen atmosphere. 3.7 g of glycidol was added dropwise. After the entire amount was dropped, stirring was continued for 5 hours. Then, it cooled with the ice bath and hydrochloric acid aqueous solution was dripped until the liquid property became acidic. After completion of the reaction, the organic phase was recovered by washing once with water and once with saturated saline. The collected liquid was concentrated with an evaporator.
- the value of F / Si represents the amount of fluorine-containing polyether adhering to the substrate, that is, the thickness of the surface layer. From the conventional knowledge, about 0.8 to 1.0 is suitable from the viewpoint of lubricity. I know that Before treatment, Examples 3 and 4 show that F / Si has a high value, that is, the surface layer is too thick and the lubricity is insufficient. On the other hand, in Examples 1 and 2, F / Si is in a desired range, that is, a suitable surface layer is formed. After the treatment, in Examples 1 and 3, F / Si is below the desired range, and the coefficient of dynamic friction shows a high value, that is, a part of the surface layer has disappeared due to the treatment. Is shown. On the other hand, Examples 2 and 4 show that the surface layer is firmly adhered to the base material because there is no change in the dynamic friction system number and F / Si before and after the treatment.
- Example 5 (Example 5-1) While the compound (10-1) represented by the following formula (10-1), triethylamine and acetonitrile are stirred, mesyl chloride is added. After confirming that the compound (10-1) is consumed by NMR, the organic phase is washed with water, and the solvent of the obtained organic phase is distilled off, whereby the following formula (11-1) is obtained. To obtain the compound (11-1). HOCH 2 CF 3 (10-1) CH 3 SO 2 —OCH 2 CF 3 (11-1)
- Example 5-2 In the same manner as in Example 1, compound (A1-1), that is, compound (13-1) represented by the following formula (13-1) is obtained. (CF 2 CF 2 O) units and (CF 2 CF 2 CF 2 CF 2 O) units are alternately arranged except for a part. Compound (13-1) may be used as the fluorine-containing polyether compound (B). HOCH 2 CF 2 CF 2 CF 2 —O — [(CF 2 CF 2 O) 7 — (CF 2 CF 2 CF 2 CF 2 O) 4 ] —CF 2 CF 2 CF 2 CH 2 OH (13- 1)
- Example 5-3 The compound (13-1) and sodium metal are sufficiently reacted in tetrahydrofuran with cooling in an ice bath, and then added dropwise to the compound (11-1). After confirming that compound (11-1) is consumed by NMR, the organic phase is washed with 0.1N hydrochloric acid, and the solvent of the obtained organic phase is distilled off. To obtain a mixture of the compounds (16-1), (16-2) and the compound (13-1). Compound (16-1) may be used as the fluorine-containing polyether compound (B).
- the target compound (16-1) is obtained by fractionating and purifying the mixture by silica gel column chromatography.
- silica gel D-50-120A, D-75-60A, etc. manufactured by AGC S-Tech are used.
- As the developing solvent Asahi Clinic AK-225, Asahi Clin AC-2000, Asahi Clin AC-6000, etc., manufactured by Asahi Glass Co., Ltd. are used as nonpolar solvents, and Asahi Clin AE-3000, ethyl acetate, acetone, ethanol, etc. are used as polar solvents. Is used.
- Silica gel is used 5 to 20 times by mass with respect to the fraction to be fractionated.
- the developing solvent is used 20 to 100 times by volume with respect to the fraction to be fractionated.
- the abundance ratios of the compounds (16-1), (16-2) and the compound (13-1) are judged by methods such as NMR and HPLC.
- Example 5-4 After sufficiently reacting compound (13-1) and metallic sodium in tetrahydrofuran, compound (12-1) represented by the following formula (12-1) is added dropwise. A mixture of the compounds (15-1), (15-2) and the compound (13-1) represented by the following formula is obtained. However, Ph is a phenyl group. Compounds (15-1) and (15-2) may be used as the fluorinated polyether compound (B).
- the mixture is fractionated and purified by silica gel column chromatography to obtain the target compound (15-1).
- silica gel D-50-120A, D-75-60A, etc. manufactured by AGC S-Tech are used.
- As the developing solvent Asahi Clinic AK-225, Asahi Clin AC-2000, Asahi Clin AC-6000, etc., manufactured by Asahi Glass Co., Ltd. are used as nonpolar solvents, and Asahi Clin AE-3000, ethyl acetate, acetone, ethanol, etc. are used as polar solvents. Is used.
- Silica gel is used 5 to 20 times by mass with respect to the fraction to be fractionated.
- the developing solvent is used 20 to 100 times by volume with respect to the fraction to be fractionated.
- the abundance ratios of the compounds (15-1), (15-2) and the compound (13-1) are judged by methods such as NMR and HPLC.
- Example 5-6 The compound (15-1) and sodium metal are sufficiently reacted in tetrahydrofuran and then added dropwise to the compound (18-1). After confirming that the compound (18-1) is consumed by NMR, the organic phase is washed with 0.1N hydrochloric acid, and the solvent of the obtained organic phase is distilled off. To obtain a mixture of the compounds (19-1), (A61-1) and the compound (18-1).
- the target compounds (19-1) and (A61-1) are obtained by fractionating and purifying the mixture by silica gel column chromatography.
- silica gel D-50-120A, D-75-60A, etc. manufactured by AGC S-Tech are used.
- As the developing solvent Asahi Clinic AK-225, Asahi Clin AC-2000, Asahi Clin AC-6000, etc., manufactured by Asahi Glass Co., Ltd. are used as nonpolar solvents, and Asahi Clin AE-3000, ethyl acetate, acetone, ethanol, etc. are used as polar solvents. Is used.
- Silica gel is used 5 to 20 times by mass with respect to the fraction to be fractionated.
- the developing solvent is used 20 to 100 times by volume with respect to the fraction to be fractionated.
- the abundance ratios of the compounds (19-1), (A61-1) and the compound (18-1) are determined by methods such as NMR and HPLC.
- Example 6 (Example 6-1) Attach a reflux tube to a 300 mL three-necked flask, add 0.3 mol of compound (15-1), 0.33 mol of metallic sodium, and 100 mL of dehydrated tetrahydrofuran at 70 ° C. until the metallic sodium is consumed. Continue stirring. After the disappearance of the metal sodium, 0.1 mol of cyclotrimer of phosphonitrile chloride is added and reacted at 70 ° C., and consumption of the compound (15-1) is confirmed by NMR to complete the reaction.
- Example 6-2 Attach a reflux tube to a 300 mL three-necked flask, add 0.3 mol of compound (16-1), 0.33 mol of metallic sodium, and 100 mL of dehydrated tetrahydrofuran at 70 ° C. until the metallic sodium is consumed. Continue stirring. After the metal sodium has disappeared, a mixture of the compound (20-1) is added and reacted in the same manner at 70 ° C. The consumption of the compound (20-1) is confirmed by NMR, and the reaction is completed.
- Example 7 Compound (21-1) represented by the following formula (21-1) (manufactured by NOF Corporation, polyserine (registered trademark) DC-1100, (CF 2 CF 2 O) unit and (CF 2 CF 2 CF 2 O) Units are randomly arranged.) Sodium fluoride is added to the mixture, and the mixture is sufficiently stirred. After the compound (5-2) represented by the following formula (5-2) is added dropwise, To react. After confirming that the compound (21-1) was consumed by NMR, sodium fluoride was removed with a pressure filter, and the excess compound (5-2) was distilled off under reduced pressure to give the following formula (22-1 ) Is obtained.
- formula (21-1) manufactured by NOF Corporation, polyserine (registered trademark) DC-1100, (CF 2 CF 2 O) unit and (CF 2 CF 2 CF 2 O) Units are randomly arranged.
- Sodium fluoride is added to the mixture, and the mixture is sufficiently stirred. After the compound (5-2) represented by the following formula
- Example 7-2 R-113 (CF 2 ClCFCl 2 ) is charged into an autoclave (made of nickel), nitrogen gas is blown at 25 ° C. for 1 hour, and then 20% fluorine gas is blown at 25 ° C. for 1 hour. With 20% fluorine gas blown at the same flow rate, the compound (22-1) is diluted to R-113 and continuously fed. When the feeding is completed, the internal pressure is increased to 0.15 MPa (gauge pressure), and the mixture is heated from 25 ° C. to 40 ° C. and stirred. After confirming that no hydrogen atoms remain by NMR, nitrogen gas is blown at 25 ° C. for 1 hour to complete the reaction.
- 0.15 MPa gauge pressure
- Example 7-3 The compound (23-1) is stirred while being cooled in an ice bath, methanol is slowly added dropwise under a nitrogen atmosphere, and the mixture is stirred for 12 hours while bubbling with nitrogen. After confirming the consumption of the compound (23-1) by NMR, the solvent is distilled off from the reaction solution to obtain a mixture of the compounds (24-1i) to (24-1iii) represented by the following formula. Compounds (24-1i) to (24-1iii) may be used as the fluorine-containing polyether compound (B).
- Example 7-4 A reactor in which a mixture of ethanol, lithium chloride, and compounds (24-1i) to (24-1iii) is stirred while being cooled in an ice bath, and sodium borohydride powder is dispersed in ethanol under a nitrogen atmosphere Is dripped. After dripping the whole amount, slowly warm to room temperature and continue stirring. After confirming that the compounds (24-1i) to (24-1iii) were consumed by NMR, the solution was cooled again in an ice bath and 0.1N hydrochloric acid and asahiklin AK-225 until the liquid became acidic. And the organic phase is recovered. The organic phase is recovered after washing twice with water again.
- the solvent is distilled off from the collected organic phase to obtain a mixture of compounds (13a-1i) to (13a-1iii).
- Compounds (13a-1i) to (13a-1iii) may be used as the fluorinated polyether compound (B).
- Example 8 Compound (25-1) represented by the following formula (25-1) (manufactured by NOF Corporation, PEG # 200) and compound (26-1) represented by the following formula (26-1) (manufactured by NOF Corporation) And Uniol (registered trademark) PB-500).
- Example 8-2 After sufficiently reacting compound (26-1) and metallic sodium in tetrahydrofuran with cooling in an ice bath, compound (27-1) is added dropwise. Alternatively, compound (25-1) and metal sodium are sufficiently reacted in tetrahydrofuran with cooling with an ice bath, and then compound (28-1) is added dropwise. At this time, the alkoxide of the compound (26-1) or the compound (25-1) is preferably present in a large excess amount relative to the dropped compound (27-1) or the compound (28-1). -1) or the dropping rate of compound (28-1) is preferably sufficiently slow for the reaction.
- Example 8-3 Sodium fluoride is added to the compound (29-1i) or the compound (29-1ii), the mixture is sufficiently stirred, and the compound (5-2) is added dropwise, followed by sufficient reaction at room temperature. After confirming that compound (29-1i) or compound (29-1ii) was consumed by NMR, sodium fluoride was removed with a pressure filter, and excess compound (5-2) was distilled off under reduced pressure.
- the compound (30-1i) represented by the following formula (30-1i) or the compound (30-1ii) represented by the following formula (30-1ii) is obtained.
- Example 8-4 R-113 (CF 2 ClCFCl 2 ) is charged into an autoclave (made of nickel), nitrogen gas is blown at 25 ° C. for 1 hour, and then 20% fluorine gas is blown at 25 ° C. for 1 hour. In a state where 20% fluorine gas is blown at the same flow rate, the compound (30-1i) or the compound (30-1ii) is diluted to R-113 and continuously fed. When the feeding is completed, the internal pressure is increased to 0.15 MPa (gauge pressure), and the mixture is heated from 25 ° C. to 40 ° C. and stirred. After confirming that no hydrogen atoms remain by NMR, nitrogen gas is blown at 25 ° C. for 1 hour to complete the reaction.
- 0.15 MPa gauge pressure
- Example 8-5 The compound (31-1i) or the compound (31-1ii) is stirred while being cooled in an ice bath, methanol is slowly added dropwise under a nitrogen atmosphere, and the mixture is stirred for 12 hours while bubbling with nitrogen. After confirming the consumption of compound (31-1i) or compound (31-1ii) by NMR, the solvent is distilled off from the reaction solution, whereby compound (32-1i) represented by the following formula (32-1i) Alternatively, a compound (32-1ii) represented by the following formula (32-1ii) is obtained.
- Compounds (32-1i) and (32-1ii) may be used as the fluorine-containing polyether compound (B).
- Example 8-6 A reactor was charged with ethanol, lithium chloride, compound (32-1i) or compound (32-1ii), stirred while cooling in an ice bath, and sodium borohydride powder dispersed in ethanol under a nitrogen atmosphere. Dripping. After dripping the whole amount, slowly warm to room temperature and continue stirring. After confirming that compound (32-1i) or compound (32-1ii) has been consumed by NMR, it is cooled again in an ice bath and 0.1N hydrochloric acid and asahiklin AK- are used until the liquid becomes acidic. 225 is added and the organic phase is recovered. The organic phase is recovered after washing twice with water again.
- the fluorine-containing polyether compound of the present invention is useful as a surface modifier (such as a lubricant) or a surfactant, and is applied on a diamond-like carbon protective film (DLC film) of a magnetic disk to impart lubricity. It is particularly useful as a lubricant.
- a surface modifier such as a lubricant
- DLC film diamond-like carbon protective film
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Abstract
Description
また、磁気ディスクからの情報の読み取り速度および磁気ディスクへの情報の書き込み速度の高速化にともない、磁気ディスクの回転は速くなってきている。そのため、表面層には、高速回転する磁気ディスクから飛散しないように炭素保護膜への密着性の向上が要求されている。
(1)4価の連結基に結合した4本のポリ(オキシペルフルオロアルキレン)鎖を有し、該鎖が(CF2CF2O)単位のみからなり、該鎖の末端にHOCH2CH(OH)CH2OCH2CF2-基を有する含フッ素ポリエーテル化合物(特許文献1)。
(2)3価以上の連結基に結合した3本以上のポリ(オキシペルフルオロアルキレン)鎖を有し、該鎖が(CF2CF2O)単位のみからなり、少なくとも2つの該鎖の末端にHOCH2CF2-基、HOCH2CH(OH)CH2OCH2CF2-基等を有する含フッ素ポリエーテル化合物(特許文献2)。
[1]下式(A)で表される含フッ素ポリエーテル化合物。
{X-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]}m-Y-{[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-Z}n ・・・(A)
ただし、
Xは、水酸基、カルボキシ基、エステル基またはアリール基を有する基であり、
Yは、末端にエーテル性酸素原子を有しない、(m+n)価の連結基であり、
Zは、水酸基、カルボキシ基、エステル基およびアリール基を有さず、かつハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)または炭素原子-炭素原子間にエーテル性酸素原子が挿入されたハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)を有する基であり、
mは、1~10の整数であり、
nは、0~10の整数であり、
m+nは、2~20の整数であり、
a、b、c、dは、それぞれ独立に1~100の整数であり、
[(CF2CF2O)a-(CF2CF2CF2CF2O)b]中のa個の(CF2CF2O)単位およびb個の(CF2CF2CF2CF2O)単位の結合順序、および、[(OCF2CF2)c-(OCF2CF2CF2CF2)d]中のc個の(OCF2CF2)単位およびd個の(OCF2CF2CF2CF2)単位の結合順序、は限定されない。
[3]b/(a+b)が0.2~0.8であり、d/(c+d)が0.2~0.8である、[1]または[2]の含フッ素ポリエーテル化合物。
[4](OCF2CF2)単位と(OCF2CF2CF2CF2)単位とが交互に配置された構造を有する、[1]~[3]のいずれかの含フッ素ポリエーテル化合物。
[5]Xが、HOCH2CH(OH)CH2OCH2CF2CF2CF2-基またはHOCH2CH(OH)CH2OCH2CF2-基である、[1]~[4]のいずれかの含フッ素ポリエーテル化合物。
X-O-[(CF2CF2O)g-(CF2CF2CF2CF2O)h]-W ・・・(B)
ただし、
Xは、水酸基、カルボキシ基、エステル基またはアリール基を有する基であり、
Wは、水酸基、カルボキシ基、エステル基、アリール基、またはハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)もしくは炭素原子-炭素原子間にエーテル性酸素原子が挿入されたハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)を有する基であり、
g、hは、それぞれ独立に1~200の整数であり、
[(CF2CF2O)g-(CF2CF2CF2CF2O)h]中のg個の(CF2CF2O)単位およびh個の(CF2CF2CF2CF2O)単位の結合順序は限定されない。
[8]h/(g+h)が0.2~0.8である、[6]または[7]の含フッ素ポリエーテル化合物。
[9](CF2CF2O)単位と(CF2CF2CF2CF2O)単位とが交互に配置された構造を有する、[6]~[8]のいずれかの含フッ素ポリエーテル化合物。
[10]Xが、HOCH2CH(OH)CH2OCH2CF2CF2CF2-基またはHOCH2CH(OH)CH2OCH2CF2-基である、[6]~[9]のいずれかの含フッ素ポリエーテル化合物。
[12]前記[1]~[10]のいずれかの含フッ素ポリエーテル化合物と液状媒体とを含む、液状組成物。
[13]基材上に、前記[1]~[10]のいずれかの含フッ素ポリエーテル化合物を含む膜を有する、物品。
本発明の物品は、基材上に潤滑性に優れる膜を有する。
「アルカン基」とは、アルカンから水素原子を1個以上除いた1価以上の基を意味する。なお、1価のアルカン基はアルキル基であり、2価のアルカン基はアルキレン基である。
「ペルフルオロ」とは、炭素原子に結合した水素原子のすべてがフッ素原子に置換されたことを意味する。
「フルオロアルカン基」とは、アルカン基の水素原子の一部またはすべてがフッ素原子に置換された基を意味する。
「ペルフルオロアルカン基」とは、アルカン基の水素原子のすべてがフッ素原子に置換された基を意味する。
「ハロアルキル基」とは、アルキル基の水素原子の一部またはすべてがフッ素原子、塩素原子またはその両方に置換された基を意味する。
「フルオロアルキル基」とは、アルキル基の水素原子の一部またはすべてがフッ素原子に置換された基を意味する。
「エステル基」とは、RC(O)O-またはROC(O)-(ただし、Rは炭化水素基である。)で表される基を意味する。
「エーテル性酸素原子」とは、炭素原子-炭素原子間においてエーテル結合(-O-)を形成する酸素原子を意味する。
「ポリエーテル鎖」とは、オキシアルキレン基(ただし、アルキルレン基の水素原子の一部またはすべてはフッ素原子、塩素原子またはその両方に置換されていてもよい。)が複数連結した、鎖状の構造の、2価の基を意味する。「ポリエーテル鎖」は、ポリ(オキシアルキレン)基、ポリ(オキシフルオロアルキレン)基、ポリ(オキシペルフルオロアルキレン)基等を包含する。
本発明の含フッ素ポリエーテル化合物の第1の態様は、下式(A)で表される含フッ素ポリエーテル化合物(A)(以下、化合物(A)とも記す。)である。
{X-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]}m-Y-{[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-Z}n ・・・(A)
Xは、水酸基、カルボキシ基、エステル基またはアリール基を有する基である。
Xを有する基の数mは、1~10の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~6が好ましい。
(X1)i-Q1- ・・・(X1)
ただし、
X1は、水酸基、カルボキシ基、エステル基またはアリール基であり、
Q1は、(i+1)価の連結基(ただし、右側に隣接する酸素原子に結合する酸素原子を有さず、X1が水酸基またはRC(O)O-基の場合は、これらに結合する酸素原子を有しない。)であり、
iは、1または2である。
HO-(CH2)jQF- ・・・(X11)
(HO)i-Q11O(CH2)jQF- ・・・(X12)
HOC(O)-QF- ・・・(X13)
R11C(O)O-(CH2)jQF- ・・・(X14)
R11OC(O)-QF- ・・・(X15)
φ-Q12O-(CH2)jQF- ・・・(X16)
ただし、
QFは、-CF2-または-CF2CF2CF2-であり、
Q11は、(i+1)価のアルカン基(アルキレン基、アルカン-トリイル基)または炭素原子-炭素原子間にエーテル性酸素原子が挿入された(i+1)価のアルカン基であり、
Q12は、単結合、-C(O)-、-NH-、アルキレン基または炭素原子-炭素原子間にエーテル性酸素原子が挿入されたアルキレン基であり、
R11は、炭素数1~20のアルキル基であり、
φは、アリール基であり、
iは、1または2であり、炭素保護膜との密着性に優れる点から、2が好ましく、
jは、1または2であり、化合物を製造しやすい点から、1が好ましい。
HOCH2CF2CF2CF2-
HOCH2CF2-
HOCH2CH2CF2CF2CF2-
HOCH2CH2CF2-
HOCH2CH(OH)CH2OCH2CF2CF2CF2-
HOCH2CH(OH)CH2OCH2CF2-
HOCH2CH2CH(OH)CH2OCH2CF2CF2CF2-
HOCH2CH2CH(OH)CH2OCH2CF2-
HOCH2CH2CH2CH(OH)CH2OCH2CF2CF2CF2-
HOCH2CH2CH2CH(OH)CH2OCH2CF2-
HOCH2CH2OCH2CF2CF2CF2-
HOCH2CH2OCH2CF2-
HOCH2CH2CH2OCH2CF2CF2CF2-
HOCH2CH2CH2OCH2CF2-
HOCH2CH2CH2CH2OCH2CF2CF2CF2-
HOCH2CH2CH2CH2OCH2CF2-
HOC(O)CF2CF2CF2-
HOC(O)CF2-
R11C(O)OCH2CF2CF2CF2-
R11C(O)OCH2CF2-
R11OC(O)CF2CF2CF2-
R11OC(O)CF2-
HOCH2CH(OH)CH2OCH2CF2CF2CF2-
HOCH2CH(OH)CH2OCH2CF2-
Yは、末端にエーテル性酸素原子を有しない、(m+n)価の連結基である。
Yの価数m+nは、2~20の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点、さらに化合物(A)を製造しやすい点から、2~6の整数が好ましい。
-CF2CF2-
-CH2CH2-
Zは、水酸基、カルボキシ基、エステル基およびアリール基を有さず、かつハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)または炭素原子-炭素原子間にエーテル性酸素原子が挿入されたハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)を有する基である。
Zを有する基の数nは、0~10の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点、さらに化合物(A)を製造しやすい点から、0~5が好ましい。
-QF(CH2)jOR21 ・・・(Z1)
ただし、
QFは、-CF2-または-CF2CF2CF2-であり、
R21は、ハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)または炭素原子-炭素原子間にエーテル性酸素原子が挿入されたハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)であり、
jは、1または2であり、化合物を製造しやすく、化合物の安定性に優れる点から、1が好ましい。
-CH2CF3
-CH(CF3)2
-CH2CF2CHF2
-CH2CF2CF2CF3
-CH2CF2CF2CF2CHF2
-CH2CH2CF2CF2CF2CF3
-CH2CH2CF2CF2CF2CF2CF2CF3
-CH2CH2CF2CF2CF2CF2CF2CF2CF2CF3
-CH2CCl3
-CH2CH2Cl
化合物(A)におけるポリエーテル鎖は、(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とからなる。(CF2CF2O)単位のみからなるポリエーテル鎖は、柔軟性が不充分なため、該ポリエーテル鎖を有する含フッ素ポリエーテル化合物は、潤滑性が不充分である。該ポリエーテル鎖に(CF2CF2CF2CF2O)単位を導入することによって、ポリエーテル鎖が、比較的柔らかくなり、そのようなポリエーテル鎖を有する含フッ素ポリエーテル化合物は、潤滑性に優れる。
CF2CF2O)単位と(CF2CF2CF2CF2O)単位とからなるポリエーテル鎖は、ポリエーテル鎖の柔軟性が充分であって、かつポリエーテル鎖中の柔軟性の均一性に優れる点から、(OCF2CF2)単位と(OCF2CF2CF2CF2)単位とが交互に配置された構造を有することが好ましい。
aは、1~100の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~50が好ましく、1~20が特に好ましい。
bは、1~100の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~50が好ましく、1~20が特に好ましい。
-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e-
ただし、
eは、1~99の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~50が好ましく、1~20が特に好ましい。
cは、1~100の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~50が好ましく、1~20が特に好ましい。
dは、1~100の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~50が好ましく、1~20が特に好ましい。
-(OCF2CF2OCF2CF2CF2CF2)eOCF2CF2-
ただし、
eは、1~99の整数であり、化合物(A)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~50が好ましく、1~20が特に好ましい。
化合物(A)は、下記の点から、-OCF2O-構造を有しないことが好ましい。
・-OCF2O-構造を有する含フッ素ポリエーテル化合物は、-OCF2O-構造を有しない含フッ素ポリエーテル化合物に比べ、化学的な安定性が劣る。
・ポリエーテル鎖が(CF2O)単位を有すると、ポリエーテル鎖が柔軟になりすぎ、ランダムコイル状態となる。そのため、基材に塗布した場合、一部でかたまりになって盛り上がり、塗膜の薄肉化が難しい。
化合物(A)の数平均分子量は、500~50,000が好ましく、500~10,000がより好ましく、1,000~5,000が特に好ましい。化合物(A)の数平均分子量が前記下限値以上であれば、溶剤への溶解性、粘度、潤滑性に優れる。化合物(A)の数平均分子量が前記上限値以下であれば、磁気ディスク上に塗布された場合に、使用中に揮発しにくくなる。
含フッ素ポリエーテル化合物(A)の製造方法としては、たとえば、下記の方法(1)および方法(2)が挙げられる。なお、含フッ素ポリエーテル化合物(A)の製造方法は、これらに限定はされない。
(1)(m+n)個の水酸基を有するポリオールを起点とし、CF2=CFOCF2CF2CF2CH2OHを付加重合させ、フッ素化することによって(m+n)価のYで連結されたポリエーテル鎖を形成し、末端にX、必要に応じてZを導入するする方法。
(2)ポリエーテル鎖の一方の末端にXを導入した含フッ素ポリエーテル化合物、必要に応じてポリエーテル鎖の一方の末端にZを導入した含フッ素ポリエーテル化合物を用意し、(m+n)個の-SO2CH3基等を有する化合物と反応させる方法。
以下、方法(1)の例として方法(1-1)~(1-3)を説明し、方法(2)の例として方法(2-1)~(2-2)を説明する。
下式(A1)で表される化合物(A1)、下式(A2)で表される化合物(A2)および下式(A5)で表される化合物(A5)の製造方法について説明する。
{HOCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A1)
{HOCH2CH(OH)CH2OCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A2)
{R11OC(O)CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A5)
ただし、
YFは、末端にエーテル性酸素原子を有しない、(m+n)価のペルフルオロアルカン基、または炭素原子-炭素原子間にエーテル性酸素原子が挿入された(m+n)価のペルフルオロアルカン基である。
化合物(A1)におけるHOCH2CF2CF2CF2-は、基(X11)であり、
化合物(A2)におけるHOCH2CH(OH)CH2OCH2CF2CF2CF2-は、基(X12)であり、
化合物(A5)におけるR11OC(O)CF2CF2CF2-は、基(X15)である。
CF2=CFOCF2CF2CF2C(O)OCH3 ・・・(1)
CF2=CFOCF2CF2CF2CH2OH ・・・(2)
(HO)m-Y1 ・・・(3)
{HO-(CH2CF2CF2CF2OCHFCF2O)e+1}m-Y1 ・・・(4)
RfC(O)F ・・・(5)
{RfC(O)O-(CH2CF2CF2CF2OCHFCF2O)e+1}m-Y1 ・・・(6)
{RfC(O)O-(CF2CF2CF2CF2OCF2CF2O)e+1}m-YF ・・・(7)
R11OH ・・・(8)
{R11OC(O)CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A5)
{HOCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A1)
下式(A11)で表される化合物(A11)の製造方法について説明する。
{HOCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF-{(OCF2CF2CF2CF2OCF2CF2)eOCF2CF2-O-CF2CF2CF2CH2OR21}n ・・・(A11)
HOCH2CF2CF2CF2-は、基(X11)であり、
-CF2CF2CF2CH2OR21は、基(Z1)である。
{HOCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m+n-YF ・・・(A1)
HOR21 ・・・(10)
CH3SO2-OR21 ・・・(11)
{HOCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF-{(OCF2CF2CF2CF2OCF2CF2)eOCF2CF2-O-CF2CF2CF2CH2OR21}n ・・・(A11)
下式(A6)で表される化合物(A6)の製造方法について説明する。
{φQ12OCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A6)
φQ12O(CH2)jQF-は、基(X16)である。
{HOCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A1)
φQ12-A ・・・(12)
{φQ12OCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)e}m-YF ・・・(A6)
下式(A61)で表される化合物(A61)および下式(A62)で表される化合物(A62)の製造方法について説明する。
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m+n-Y2 ・・・(A61)
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m-Y2-{O(CH2)jQF-[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-QF(CH2)jOR21}n ・・・(A62)
ただし、
Y2は、末端にエーテル性酸素原子を有さず、かつ末端がCH2である、(m+n)価のアルカン基、炭素原子-炭素原子間にエーテル性酸素原子が挿入された(m+n)価のアルカン基、(m+n)価のフルオロアルカン基、または炭素原子-炭素原子間にエーテル性酸素原子が挿入された(m+n)価のフルオロアルカン基である。
{-QF(CH2)jO}m-Y2-{O(CH2)jQF-}nは、Yに相当し、
φQ12O(CH2)jQF-は、基(X16)であり、
-QF(CH2)jOR21は、基(Z1)である。
HO(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jOH ・・・(13)
HO(CH2)jQF-[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-OQF(CH2)jOH ・・・(14)
φQ12-A ・・・(12)
φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jOH ・・・(15)
CH3SO2-OR21 ・・・(11)
HO(CH2)jQF-[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-QF(CH2)jOR21 ・・・(16)
(HO)m+n-Y2 ・・・(17)
(CH3SO2-O)m+n-Y2 ・・・(18)
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m-Y2-(O-SO2CH3)n ・・・(19)
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m+n-Y2 ・・・(A61)
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m-Y2-{O(CH2)jQF-[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-QF(CH2)jOR21}n
・・・(A62)
下式(A63)で表される化合物(A63)の混合物の製造方法について説明する。
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m1-P3N3-{O(CH2)jQF-[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-QF(CH2)jOR21}n1 ・・・(A63)
ただし、
P3N3は、シクロトリホスファゼン構造であり、
m1は、0~6の整数であり、
n1は、0~6の整数であり、
m1+n1=6である。
{-QF(CH2)jO}m1-P3N3-{O(CH2)jQF-}n1は、Yに相当し、
φQ12O(CH2)jQF-は、基(X16)であり、
-QF(CH2)jOR21は、基(Z1)である。
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m1-P3N3-(Cl)n1 ・・・(20)
{φQ12O(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jO}m1-P3N3-{O(CH2)jQF-[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-QF(CH2)jOR21}n1 ・・・(A63)
化合物(13)および化合物(14)の製造方法について、化合物(13)を例にとり説明する。化合物(14)は、化合物(13)と同様にして製造できる。
HO(CH2)jQF-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]-QF(CH2)jOH ・・・(13)
HO(CH2)jQF-[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-QF(CH2)jOH ・・・(14)
方法(3-1)は、(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とが交互に配置されている化合物(13)の製造例である。
(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とが交互に配置されている化合物(13)は、方法(1-1)によって化合物(A1)を製造する際に、化合物(3)として、下式(3-1)で表される化合物(3-1)を用いることによって製造できる。
HO-CH2CH2-OH ・・・(3-1)
方法(3-2)は、(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とがランダムに配置されている化合物(13)の製造例である。
HO-[(CH2CH2O)a1-(CH2CH2CH2CH2O)b1]-H ・・・(21)
化合物(21)の市販品としては、日油社製のポリセリン(登録商標)シリーズ(DC-1100、DC-1800E、60DC-1800、DC-3000E)等が挙げられる。
RfC(O)F ・・・(5)
RfC(O)O-[(CH2CH2O)a1-(CH2CH2CH2CH2O)b1]-C(O)Rf ・・・(22)
RfC(O)O-[(CF2CF2O)a1-(CF2CF2CF2CF2O)b1]-C(O)Rf ・・・(23)
R11OH ・・・(8)
R11OC(O)CF2CF2CF2-O-[(CF2CF2O)a1-(CF2CF2CF2CF2O)b1-2]-CF2CF2CF2C(O)OR11 ・・・(24i)
R11OC(O)CF2-O-[(CF2CF2O)a1-1-(CF2CF2CF2CF2O)b1-1]-CF2CF2CF2C(O)OR11 ・・・(24ii)
R11OC(O)CF2-O-[(CF2CF2O)a1-2-(CF2CF2CF2CF2O)b1]-CF2C(O)OR11 ・・・(24iii)
HOCH2CF2CF2CF2-O-[(CF2CF2O)a1-(CF2CF2CF2CF2O)b1-2]-CF2CF2CF2CH2OH ・・・(13ai)
HOCH2CF2-O-[(CF2CF2O)a1-1-(CF2CF2CF2CF2O)b1-1]-CF2CF2CF2CH2OH ・・・(13aii)
HOCH2CF2-O-[(CF2CF2O)a1-2-(CF2CF2CF2CF2O)b1]-CF2CH2OH ・・・(13aiii)
方法(3-3)は、複数の(CF2CF2O)単位からなる1つ以上のブロックと複数の(CF2CF2CF2CF2O)単位からなる1つ以上のブロックとが連結した化合物(13)の製造例である。
HO-(CH2CH2O)a2-H ・・・(25)
HO-(CH2CH2CH2CH2O)b2-H ・・・(26)
化合物(25)の市販品としては、日油社製のポリエチレングリコール(PEG#200T、PEG#200、PEG#300、PEG#400、PEG#600、PEG#1000、PEG#1540、PEG#2000)等が挙げられる。
化合物(26)の市販品としては、日油社製のユニオール(登録商標)シリーズ(PB-500、PB-700、PB-1000、PB-2000、PB-4800)等が挙げられる。
CH3SO2-O-(CH2CH2O)a2-SO2CH3 ・・・(27)
CH3SO2-O-(CH2CH2CH2CH2O)b2-SO2CH3 ・・・(28)
HO-(CH2CH2O)a2-(CH2CH2CH2CH2O)b2-(CH2CH2O)a2-H ・・・(29i)
HO-(CH2CH2CH2CH2O)b2-(CH2CH2O)a2-(CH2CH2CH2CH2O)b2-H ・・・(29ii)
RfC(O)F ・・・(5)
RfC(O)O-(CH2CH2O)a2-(CH2CH2CH2CH2O)b2-(CH2CH2O)a2-C(O)Rf ・・・(30i)
RfC(O)O-(CH2CH2CH2CH2O)b2-(CH2CH2O)a2-(CH2CH2CH2CH2O)b2-C(O)Rf ・・・(30ii)
RfC(O)O-(CF2CF2O)a2-(CF2CF2CF2CF2O)b2-(CF2CF2O)a2-C(O)Rf ・・・(31i)
RfC(O)O-(CF2CF2CF2CF2O)b2-(CF2CF2O)a2-(CF2CF2CF2CF2O)b2-C(O)Rf ・・・(31ii)
R11OH ・・・(8)
R11OC(O)CF2O-(CF2CF2O)a2-1-(CF2CF2CF2CF2O)b2-(CF2CF2O)a2-1-CF2C(O)OR11 ・・・(32i)
R11OC(O)CF2CF2CF2O-(CF2CF2CF2CF2O)b2-1-(CF2CF2O)a2-(CF2CF2CF2CF2O)b2-1-CF2CF2CF2C(O)OR11 ・・・(32ii)
HOCH2CF2-O-(CF2CF2O)a2-1-(CF2CF2CF2CF2O)b2-(CF2CF2O)a2-1-CF2CH2OH ・・・(13bi)
HOCH2CF2CF2CF2-O-(CF2CF2CF2CF2O)b2-1-(CF2CF2O)a2-(CF2CF2CF2CF2O)b2-1-CF2CF2CF2CH2OH ・・・(13bii)
以上説明した含フッ素ポリエーテル化合物(A)にあっては、ポリエーテル鎖が(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とからなるため、(CF2CF2O)単位のみからなるポリエーテル鎖に比べ、柔軟性に優れる。そのため、(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とからなるポリエーテル鎖を有する含フッ素ポリエーテル化合物(A)は、潤滑性に優れる。
また、含フッ素ポリエーテル化合物(A)が-OCF2O-構造を有しなければ、-OCF2O-構造を有する含フッ素ポリエーテル化合物に比べ、化学的な安定性に優れる。また、-OCF2O-構造を有する含フッ素ポリエーテル化合物に比べ、直線性が高く、ランダムコイル状態とならないため、塗膜の薄肉化に対応できる。
また、式(A)中のXがHOCH2CH(OH)CH2OCH2CF2CF2CF2-基またはHOCH2CH(OH)CH2OCH2CF2-基であれば、基材との密着性に優れる。
本発明の含フッ素ポリエーテル化合物の第2の態様は、下式(B)で表される含フッ素ポリエーテル化合物(B)(以下、化合物(B)とも記す。)である。
X-O-[(CF2CF2O)g-(CF2CF2CF2CF2O)h]-W ・・・(B)
Xは、水酸基、カルボキシ基、エステル基またはアリール基を有する基である。
Xの例示、好ましい態様については、含フッ素ポリエーテル化合物(A)のXと同様であり、詳細は省略する。
以下、含フッ素ポリエーテル化合物(A)における符号と同じ符号についても、詳細は省略する。
Wは、水酸基、カルボキシ基、エステル基、アリール基、またはハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)もしくは炭素原子-炭素原子間にエーテル性酸素原子が挿入されたハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)を有する基である。
-Q1-(X1)i ・・・(W1)
-R2 ・・・(W2)
-QF(CH2)j-OH ・・・(W11)
-QF(CH2)jOQ11-(OH)i ・・・(W12)
-QF-C(O)OH ・・・(W13)
-QF(CH2)j-OC(O)R11 ・・・(W14)
-QF-C(O)OR11 ・・・(W15)
-QF(CH2)j-OQ12-φ ・・・(W16)
-QF(CH2)jOR21 ・・・(W21)
-CF2CF2CF2CH2OCH2CH(OH)CH2OH
-CF2CH2OCH2CH(OH)CH2OH
化合物(B)におけるポリエーテル鎖は、(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とからなる。(CF2CF2O)単位のみからなるポリエーテル鎖は、柔軟性が不充分なため、該鎖を有する含フッ素ポリエーテル化合物は、潤滑性が不充分である。該鎖に(CF2CF2CF2CF2O)単位を導入することによって、ポリエーテル鎖が、比較的柔らかくなり、該鎖を有する含フッ素ポリエーテル化合物は、潤滑性に優れる。
ポリエーテル鎖は、ポリエーテル鎖の柔軟性が充分であって、かつ該鎖中の柔軟性の均一性に優れる点から、(OCF2CF2)単位と(OCF2CF2CF2CF2)単位とが交互に配置された構造を有することが好ましい。
gは、1~200の整数であり、化合物(B)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~100が好ましく、1~40が特に好ましい。
hは、1~200の整数であり、化合物(B)の溶剤への溶解性、粘度、潤滑性に優れる点から、1~100が好ましく、1~40が特に好ましい。
化合物(B)は、含フッ素ポリエーテル化合物(A)と同じ理由から、-OCF2O-構造を有しないことが好ましい。
化合物(B)の数平均分子量は、含フッ素ポリエーテル化合物(A)と同じ理由から、500~50,000が好ましく、500~10,000がより好ましく、1,000~5,000が特に好ましい。
含フッ素ポリエーテル化合物(B)は、含フッ素ポリエーテル化合物(A)と同様にして製造できる。また、含フッ素ポリエーテル化合物(A)の製造過程で得られる中間体としても得られる。
HO(CH2)jQF-O-[(CF2CF2O)g-(CF2CF2CF2CF2O)h]-QF(CH2)jOH ・・・(B1)
HOCH2CH(OH)CH2O(CH2)jQF-O-[(CF2CF2O)g-(CF2CF2CF2CF2O)h]-QF(CH2)jOCH2CH(OH)CH2OH ・・・(B2)
上述した方法(3-3)によって得られる化合物(32i)、化合物(32ii)、化合物(13bi)、化合物(13bii)も含フッ素ポリエーテル化合物(B)に該当する。
上述した方法(2-1)によって得られる化合物(15)、化合物(16)も含フッ素ポリエーテル化合物(B)に該当する。
なお、含フッ素ポリエーテル化合物(B)の製造方法は、これらに限定はされない。
以上説明した含フッ素ポリエーテル化合物(B)にあっては、ポリエーテル鎖が(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とからなるため、(CF2CF2O)単位のみからなるポリエーテル鎖に比べ、柔軟性に優れる。そのため、(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とからなるポリエーテル鎖を有する含フッ素ポリエーテル化合物(B)は、潤滑性に優れる。
また、含フッ素ポリエーテル化合物(B)が-OCF2O-構造を有しなければ、-OCF2O-構造を有する含フッ素ポリエーテル化合物に比べ、化学的な安定性に優れる。また、-OCF2O-構造を有する含フッ素ポリエーテル化合物に比べ、直線性が高く、ランダムコイル状態とならないため、塗膜の薄肉化に対応できる。
また、式(B)中のXがHOCH2CH(OH)CH2OCH2CF2CF2CF2-基またはHOCH2CH(OH)CH2OCH2CF2-基であれば、基材との密着性に優れる。
本発明の含フッ素ポリエーテル化合物は、表面改質剤または界面活性剤として有用である。表面改質剤としては、潤滑剤等が挙げられる。
表面層は、分子末端に水酸基、カルボキシ基、エステル基またはアリール基を有する本発明の含フッ素ポリエーテル化合物を含むことから、高い潤滑性を保持する。そのため、該表面層を基材上に設けることで、潤滑性等の機能を付与することができる。また、表面層は、基材に対する密着性が高く、耐久性に優れる。また、表面層は、透明であり、屈折率が低く、または耐熱性もしくは耐薬品性に優れる。
表面層の厚さは、たとえば薄膜解析用X線回折計(RIGAKU社製、ATX-G)を用いて、X線反射率法によって反射X線の干渉パターンを得て、該干渉パターンの振動周期から算出できる。
本発明の潤滑剤は、本発明の含フッ素ポリエーテル化合物を含むものである。本発明の潤滑剤は、1種の含フッ素ポリエーテル化合物(A)を単独で含んでいてもよく、式(A)中のX、Y、Z、m、n、a~dの1つ以上が異なる含フッ素ポリエーテル化合物(A)の2種以上を含んでいてもよい。また、1種の含フッ素ポリエーテル化合物(B)を単独で含んでいてもよく、式(B)中のX、W、g、hの1つ以上が異なる含フッ素ポリエーテル化合物(B)の2種以上を含んでいてもよい。また、含フッ素ポリエーテル化合物(A)と含フッ素ポリエーテル化合物(B)とを含んでいてもよい。
本発明の潤滑剤は、本発明の含フッ素ポリエーテル化合物のみからなるものでもよく、他の成分をさらに含むものであってもよい。
本発明の潤滑剤における本発明の含フッ素ポリエーテル化合物の含有量は、潤滑剤の総質量に対し、90~100質量%が好ましく、100質量%が特に好ましい。すなわち、本発明の潤滑剤は、本発明の含フッ素ポリエーテル化合物のみからなるのが特に好ましい。
磁気ディスクとしては、たとえば、NiPメッキされた基板(アルミニウム、ガラス等。)上に、下地層、磁気記録層、ダイヤモンド状炭素保護膜(DLC膜)を順に有するものが挙げられる。DLC膜の厚さは、5nm以下が好ましい。DLC膜の平均表面粗さ(Ra)は、2nm以下が好ましい。
本発明の液状組成物は、本発明の含フッ素ポリエーテル化合物と、液状媒体とを含むものである。
本発明の液状組成物は、溶液、懸濁液、または乳化液のいずれであってもよく、溶液であるのが好ましい。
液状組成物中の本発明の含フッ素ポリエーテル化合物の濃度は、用途に応じて適宜調節でき、液状組成物の総質量に対し、0.005~50質量%であることが好ましく、0.005~5質量%がより好ましく、0.01~1質量%が特に好ましい。本発明の含フッ素ポリエーテル化合物の濃度が前記範囲内であると、均一な表面層を形成できる。
フルオロアルカンとしては、炭素数4~8の化合物が好ましい。市販品としては、たとえばC6F13H(旭硝子社製、AC-2000)、C6F13C2H5(旭硝子社製、AC-6000)、C2F5CHFCHFCF3(デュポン社製、バートレル(登録商標)XF)等が挙げられる。
フルオロ芳香族化合物としては、たとえばヘキサフルオロベンゼン、トリフルオロメチルベンゼン、ペルフルオロトルエン、ビス(トリフルオロメチル)ベンゼン等が挙げられる。
フルオロアルキルエーテルとしては、炭素数4~12の化合物が好ましい。フルオロアルキルエーテルとしては、ヒドロフルオロアルキルエーテルが好ましい。市販品としては、たとえばCF3CH2OCF2CF2H(旭硝子社製、AE-3000)、C4F9OCH3(3M社製、ノベック(登録商標)-7100)、C4F9OC2H5(3M社製、ノベック(登録商標)-7200)、C6F13OCH3(3M社製、ノベック(登録商標)-7300)等が挙げられる。
フルオロアルキルアミンとしては、ペルフルオロアルキルアミンが好ましく、たとえばペルフルオロトリプロピルアミン、ペルフルオロトリブチルアミン等が挙げられる。
フルオロアルコールとしては、たとえば2,2,3,3-テトラフルオロプロパノール、2,2,2-トリフルオロエタノール、ヘキサフルオロイソプロパノール等が挙げられる。
フッ素系有機溶媒としては、含フッ素ポリエーテル化合物の溶解性の点で、フルオロアルカン、フルオロ芳香族化合物、フルオロアルキルエーテルが好ましい。これらの中でも、オゾン破壊係数が低い点で、ヒドロフルオロアルキルエーテルが特に好ましい。
炭化水素系有機溶媒としては、ヘキサン、へプタン、シクロヘキサン等が好ましい。
アルコール系有機溶媒としては、メタノール、エタノール、プロパノール、イソプロパノール等が好ましい。
ケトン系有機溶媒としては、アセトン、メチルエチルケトン、メチルイソブチルケトン等が好ましい。
エーテル系有機溶媒としては、ジエチルエーテル、テトラヒドロフラン、テトラエチレングリコールジメチルエーテル等が好ましい。
エステル系有機溶媒としては、酢酸エチル、酢酸ブチル等が好ましい。
非フッ素系有機溶媒としては、含フッ素ポリエーテル化合物の溶解性の点で、ケトン系有機溶媒が特に好ましい。
液状媒体としては、フッ素系有機溶媒であるフルオロアルカン、フルオロ芳香族化合物、フルオロアルキルエーテル、非フッ素系有機溶媒である水素原子、炭素原子および酸素原子のみからなる化合物からなる群から選択される少なくとも1種の有機溶媒を、合計で液状媒体全体の90質量%以上含むことが、含フッ素ポリエーテル化合物の溶解性を高める点で好ましい。
他の成分としては、ラジカルスカベンジャー(たとえばDow Chemicals社製、X-1p)等が挙げられる。
金属イオン類(Na、K、Ca、Al等。)は、陰イオンと結合してルイス酸触媒を生成し、含フッ素ポリエーテル化合物の分解反応を促進する場合がある。陰イオン類(F、Cl、NO2、NO3、PO4、SO4、C2O4等。)および水分は、基材の表面を腐食させる場合がある。よって、液状組成物中の含水率は、2,000ppm以下が好ましい。
低分子極性化合物(アルコール類;樹脂から溶出する可塑剤等。)は、基材と表面層との密着性を低減させる場合がある。
含フッ素ポリエーテル化合物や液状組成物の使用方法は、目的に応じ公知の方法を適用できる。
たとえば本発明の含フッ素ポリエーテル化合物を、潤滑剤として使用する場合には、本発明の含フッ素ポリエーテル化合物を基材上に塗布することによって、または本発明の含フッ素ポリエーテル化合物を含む液状組成物を基材上に塗布し、乾燥すること(すなわち、液状組成物から液状媒体を除去すること)によって、本発明の含フッ素ポリエーテル化合物を含む膜(表面層)を形成させて、目的とする機能を発現させるのが好ましい。
本発明の含フッ素ポリエーテル化合物やそれを含む液状組成物を塗布する基材は特に限定されず、たとえば表面層を設ける基材として前記で挙げたものと同様のものが挙げられる。基材としては、本発明の有用性の点で、磁気ディスクが好ましい。
液状組成物を塗布した場合、乾燥方法としては、たとえば自然乾燥、真空乾燥、遠心乾燥、加熱乾燥等が挙げられる。
密着処理としては、加熱処理、赤外線照射処理、紫外線照射処理、プラズマ処理等が挙げられ、加熱処理または紫外線照射処理が好ましく、加熱処理が特に好ましい。乾燥処理が密着処理を兼ねてもよい。
さらに、密着処理後の基材を、付着物の除去、余剰の含フッ素ポリエーテル化合物の除去を目的に、フッ素系有機溶媒にて洗浄してもよい。
本発明の物品は、基材上に、本発明の含フッ素ポリエーテル化合物を含む膜を有するものである。
本発明の液状組成物を塗布する基材は特に限定されず、たとえば表面層を設ける基材として前記で挙げたものと同様のものが挙げられる。基材としては、本発明の有用性の点で、磁気ディスクが好ましい。
該膜を基材上に設ける方法としては、含フッ素ポリエーテル化合物からなる膜の形成方法として公知の方法が利用できる。たとえば上述した本発明の液状組成物を基材上に液状組成物を塗布して表面層を形成する方法等によって該膜を形成できる。
例1、2、5~8は実施例であり、例3、4は比較例である。
各例における評価方法を以下に示す。
(GPC分析)
数平均分子量(Mn)および分子量分布(Mw/Mn)は、ゲルパーミエーションクロマトグラフィ(以下、GPCとも記す。)によって測定した。なお、Mwは質量平均分子量を示す。
GPCによる測定は、特開2001-208736号公報に記載の方法にしたがい、下記条件にて行った。
移動相:R-225(旭硝子社製、アサヒクリンAK-225SECグレード1)およびヘキサフルオロイソプロピルアルコールの混合溶媒(R-225:ヘキサフルオロイソプロピルアルコール=99:1(体積比))。
分析カラム:PLgel MIXED-Eカラム(ポリマーラボラトリーズ社製)を2本直列に連結したもの。
分子量測定用標準試料:Mw/Mnが1.1未満で、Mnが2,000~10,000のペルフルオロポリエーテル4種、およびMw/Mnが1.1以上で、Mnが1,300のペルフルオロポリエーテル1種。
移動相流速:1.0mL/分。
カラム温度:37℃。
検出器:蒸発光散乱検出器。
基材上に表面層を設けた物品の最表面(物品の表面のうち表面層を設けた場所)の動摩擦係数は、摩擦測定器(Heidon社製、Tribogear)を用いて測定した。接触子としてはφ10mmのSUS製の球を用い、荷重100g、移動距離20mm、移動速度1mm/秒にて測定した。下記の基準にて評価した。
○(良好):動摩擦係数が1.7以下である。
×(不良):動摩擦係数が1.7超である。
基材(シリコンウェハ)上に設けた表面層の被覆率は、X線光電子分光法(XPS:X-ray Photoelectron Spectroscopy)により下記の測定条件にて測定されるF/Siにより下記の基準にて評価した。
○(良好):F/Siが0.8~1.0である。
×(不良):F/Siが0.8未満、または1.0超である。
試料より放出される光電子の運動エネルギーEkは、入射X線のエネルギーhν(h:プランク定数、ν:振動数)から結合エネルギーEbおよび仕事関数Wを減じた値(Ek=hν-Eb-W)である。結合エネルギーEbは、光電子が試料中で捕獲されていた原子の種類、電子軌道、化学結合状態に依存する値である。入射X線のエネルギーhνおよび仕事関数Wは既知である。そのため、運動エネルギーEkを測定すれば、結合エネルギーEbを求めることができ、試料中の原子の種類・電子軌道・化学結合状態を知ることができる。
入射X線は試料の深さ数μm程度まで侵入する。しかし、深い場所にある原子より放出された電子は、試料中の他の原子に束縛されている電子との非弾性散乱等によりエネルギーを失い、試料より放出されない。そのため、非弾性平均自由行程(電子が非弾性散乱を起こさずに進める距離)で決まる、数nm程度の深さの極く最表面から放出された電子が、光電子として観測される。したがって、XPSは、試料の最表面に存在する原子の種類や量、化学結合状態を高感度に測定する方法であり、基材上に塗布された極く薄い膜を高感度に検出でき、薄膜の被覆率を評価するのに有効な方法である。
後述する各例で得た物品(基材としてシリコンウェハを用い、基材上に、含フッ素ポリエーテル化合物を含む潤滑剤で表面層を設けた物品)の最表面のXPS測定を行うと、基材上において表面層で被覆されている箇所では、表面層中のフッ素原子の1s軌道から放出される光電子強度(以下、F1sピーク強度と記す。)は強く検出され、基材中のシリコン原子のSi2p軌道から放出される光電子強度(以下、Si2pピーク強度と記す。)は弱く検出されるかあるいは検出されない。これに対し、基材上において表面層で被覆されていない箇所では、フッ素原子から放出される光電子は検出されず、シリコン原子のSi2p軌道から放出される光電子強度が強く検出される。したがって、XPS測定により得られたF1sピーク強度とSi2pピーク強度とから算出されるF原子濃度とSi原子濃度の比は、基材上に設けた表面層の被覆率と正の相関があると考えることができる。
(例1-1)
300mLの3つ口丸底フラスコに、水素化ホウ素ナトリウム粉末の14.1gを取り入れ、AK-225(旭硝子社製)の350gを加えた。氷浴で冷却しながら撹拌し、窒素雰囲気下、内温が10℃を超えないように化合物(1)の100g、メタノールの15.8g、AK-225の22gを混合した溶液を滴下漏斗からゆっくり滴下した。全量滴下した後、さらにメタノールの10gとAK-225の10gを混合した溶液を滴下した。その後、氷浴を取り外し、室温までゆっくり昇温しながら撹拌を続けた。室温で12時間撹拌後、再び氷浴で冷却し、液性が酸性になるまで塩酸水溶液を滴下した。反応終了後、水で1回、飽和食塩水で1回洗浄し、有機相を回収した。回収した有機相を硫酸マグネシウムで乾燥した後、固形分をフィルタによりろ過し、ろ液をエバポレータで濃縮した。回収した濃縮液を減圧蒸留し、化合物(2)の80.6g(収率88%)を得た。
CF2=CFOCF2CF2CF2C(O)OCH3 ・・・(1)
CF2=CFOCF2CF2CF2CH2OH ・・・(2)
1H-NMR(300.4MHz、溶媒:重クロロホルム、基準:テトラメチルシラン(以下、TMSと記す。)) δ(ppm):2.2(1H)、4.1(2H)。
19F-NMR(282.7MHz、溶媒:重クロロホルム、基準:CFCl3) δ(ppm):-85.6(2F)、-114.0(1F)、-122.2(1F)、-123.3(2F)、-127.4(2F)、-135.2(1F)。
還流冷却器を接続した500mLのナスフラスコに、化合物(2)の100g、化合物(3-1)の11.0g、炭酸カリウム粉末の25.2gを加えた。窒素雰囲気下、75℃で1時間撹拌した後、120℃まで昇温し、内温が130℃以下になるように制御しながら、化合物(2)の200gを滴下した。全量滴下した後、120℃でさらに1時間撹拌した。NMRで化合物(2)のビニルエーテル基が完全に消失したことを確認した。塩酸水溶液を加えて、過剰の炭酸カリウムを処理し、水とAK-225を加えて分液処理を行った。3回の水洗後、有機相を回収し、エバポレータで濃縮することによって、下式(4-1)で表される化合物(4-1)の310gを得た。再び、AK-225の110gで希釈し、シリカゲルカラムクロマトグラフィ(展開溶媒:AK-225、酢酸エチル)に展開して分取し、不純物の除去、分子量の精製を行うことで化合物(4-1)の150gを得た。
HO-CH2CH2-OH ・・・(3-1)
HO-(CH2CF2CF2CF2OCHFCF2O)3-CH2CH2-(OCF2CHFOCF2CF2CF2CH2)3-OH ・・・(4-1)
1H-NMR(300.4MHz、溶媒:重アセトン、基準:TMS) δ(ppm):3.4~4.0(8H)、4.3(8H)、5.8~7.0(6H)。
19F-NMR(282.7MHz、溶媒:重アセトン、基準:CFCl3) δ(ppm):-84.3~-85.1(12F)、-89.4~-90.5(12F)、-120.2(8F)、-122.0(4F)、-126.6(8F)、-127.0(4F)、-145.1(6F)。
還流冷却器を接続した300mLのナスフラスコに、化合物(4-1)の100g、フッ化ナトリウム粉末の9.0gを取り入れ、下式(5-1)で表される化合物(5-1)の40gを加えた。窒素雰囲気下、50℃で13時間撹拌した後、70℃で3時間撹拌した。加圧ろ過器でフッ化ナトリウム粉末を除去した後、過剰の化合物(5-1)とAK-225を減圧留去し、下式(6-1)で表される化合物(6-1)の130g(収率97%)を得た。
CF3CF2CF2OCF(CF3)C(O)F ・・・(5-1)
CF3CF2CF2OCF(CF3)C(O)O-(CH2CF2CF2CF2OCHFCF2O)3-CH2CH2-(OCF2CHFOCF2CF2CF2CH2)3-OC(O)CF(CF3)OCF2CF2CF3 ・・・(6-1)
1H-NMR(300.4MHz、溶媒:重クロロホルム、基準:TMS) δ(ppm):3.4~4.0(8H)、4.3(4H)、4.9(4H)、5.8~7.0(6H)。
19F-NMR(282.7MHz、溶媒:重クロロホルム、基準:CFCl3) δ(ppm):-80.0(1F)、-81.9(3F)、-82.7(3F)、-84.7~-85.0(12F)、-86.0(1F)、-90.5~-93.0(12F)、-121.1(4F)、-121.5(8F)、-128.0(12F)、-130.3(2F)、-132.5(1F)、-145.3(6F)。
オートクレーブ(ニッケル製、内容積1L)を用意し、オートクレーブのガス出口に、0℃に保持した冷却器、NaFペレット充填層、および-10℃に保持した冷却器を直列に設置した。また-10℃に保持した冷却器から凝集した液をオートクレーブに戻す液体返送ラインを設置した。
オートクレーブにR-113(CF2ClCFCl2)の750gを投入し、25℃に保持しながら撹拌した。オートクレーブに窒素ガスを25℃で1時間吹き込んだ後、窒素ガスで20体積%に希釈したフッ素ガス(以下、20%フッ素ガスと記す。)を、25℃、流速3.2L/時間で1時間吹き込んだ。次いで、20%フッ素ガスを同じ流速で吹き込みながら、オートクレーブに、化合物(6-1)の130gをR-113の448gに溶解した溶液を、22時間かけて注入した。
次いで、20%フッ素ガスを同じ流速で吹き込みながら、オートクレーブの内圧を0.15MPa(ゲージ圧)まで加圧した。オートクレーブ内に、R-113中に0.015g/mLのベンゼンを含むベンゼン溶液の8mLを、25℃から40℃にまで加熱しながら注入し、オートクレーブのベンゼン溶液注入口を閉めた。20分撹拌した後、再びベンゼン溶液の4mLを、40℃を保持しながら注入し、注入口を閉めた。同様の操作をさらに7回繰り返した。ベンゼンの注入総量は0.6gであった。
さらに、20%フッ素ガスを同じ流速で吹き込みながら、1時間撹拌を続けた。次いで、オートクレーブ内の圧力を大気圧にして、窒素ガスを1時間吹き込んだ。オートクレーブの内容物をエバポレータで濃縮し、下式(7-1)で表される化合物(7-1)の145g(収率98%)を得た。
CF3CF2CF2OCF(CF3)C(O)O-(CF2CF2CF2CF2OCF2CF2O)3-CF2CF2-(OCF2CF2OCF2CF2CF2CF2)3-OC(O)CF(CF3)OCF2CF2CF3 ・・・(7-1)
19F-NMR(282.7MHz、溶媒:重クロロホルム、基準:CFCl3) δ(ppm):-80.0(1F)、-82.0~-82.5(6F)、-84.0(24F)、-87.8(4F)、-89.2(28F)、-126.5(24F)、-130.4(2F)、-132.4(1F)。
500mLのテトラフルオロエチレン-ペルフルオロ(アルコキシビニルエーテル)共重合体(PFA)製丸底ナスフラスコに、化合物(7-1)の145gを入れた。氷浴で冷却しながら撹拌し、窒素雰囲気下、メタノールの35gを滴下漏斗からゆっくり滴下した。窒素でバブリングしながら12時間撹拌した。反応混合物をエバポレータで濃縮し、下式(A5-1)で表される化合物(A5-1)の108g(収率100%)を得た。
CH3OC(O)CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)2-CF2CF2-(OCF2CF2OCF2CF2CF2CF2)2OCF2CF2-O-CF2CF2CF2C(O)OCH3 ・・・(A5-1)
1H-NMR(300.4MHz、溶媒:重クロロホルム、基準:TMS) δ(ppm):3.9(6H)。
19F-NMR(282.7MHz、溶媒:重クロロホルム、基準:CFCl3) δ(ppm):-84.0(28F)、-89.2(28F)、-119.8(4F)、-126.5(24F)。
300mLの3つ口丸底フラスコに、エタノールの200g、リチウムクロリドの2.1g、化合物(A5-1)の100gを取り入れ、氷浴で冷却しながら撹拌し、窒素雰囲気下、水素化ホウ素ナトリウム粉末の9.5gをエタノール200gに溶解させたものを滴下した。全量滴下した後、氷浴を取り外し、室温までゆっくり昇温しながら12時間撹拌を続けた。その後、再び氷浴で冷却し、液性が酸性になるまで塩酸水溶液を滴下した。反応終了後、水で1回、飽和食塩水で1回洗浄し、有機相を回収した。回収した液をエバポレータで濃縮した。回収した濃縮液を減圧蒸留し、得られた粗生成物を特開2009-197210号公報の実施例に記載の方法でシリカゲルカラムで精製した後、特開2009-197210号公報の実施例に記載の方法で超臨界精製し、下式(A1-1)で表される化合物(A1-1)の95g(収率98%)得た。化合物(A1-1)の数平均分子量は、2,100であり、分子量分布は1.05であった。
HOCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)2-CF2CF2-(OCF2CF2OCF2CF2CF2CF2)2OCF2CF2-O-CF2CF2CF2CH2OH ・・・(A1-1)
1H-NMR(300.4MHz、溶媒:重クロロホルム、基準:TMS) δ(ppm):4.1(4H)。
19F-NMR(282.7MHz、溶媒:重クロロホルム、基準:CFCl3) δ(ppm):-84.0(28F)、-89.2(28F)、-123.3(4F)、-126.5(24F)。
化合物(A1-1)を、濃度が0.05質量%となるようにバートレル(登録商標)XF(デュポン社製)に溶解して液状組成物を調製した。
液状組成物をシリコンウェハにディップコートで塗布して物品(表面層付き基材)を得た。ディップコータとしてはマイクロスピードディップコータ(SDI社製)を用い、10mm/秒の速さでディッピングし、60秒間浸漬した後に、2mm/秒の速さで引き揚げた。引き揚げたシリコンウェハを150℃のオーブンで10分間加熱して表面層を形成し、物品を得た。
300mLの3つ口丸底フラスコに、tert-ブチルアルコールの50g、カリウムtert-ブトキシドの5.6g、精製前の(粗生成物としての)化合物(A1-1)の100gを取り入れ、80℃に加熱しながら撹拌し、窒素雰囲気下、グリシドール(化合物(9))の7.4gを滴下した。全量滴下した後、5時間撹拌を続けた。その後、氷浴で冷却し、液性が酸性になるまで塩酸水溶液を滴下した。反応終了後、水で1回、飽和食塩水で1回洗浄し、有機相を回収した。回収した液をエバポレータで濃縮した。回収した濃縮液を減圧蒸留し、例1と同様にして精製を行い、下式(A2-1)で表される化合物(A2-1)の100g(収率93%)を得た。化合物(A2-1)の数平均分子量は、2,200であり、分子量分布は1.05であった。化合物(A2-1)を用いた以外は、例1と同様にして物品を得た。
HOCH2CH(OH)CH2OCH2CF2CF2CF2-O-CF2CF2O(CF2CF2CF2CF2OCF2CF2O)2-CF2CF2-(OCF2CF2OCF2CF2CF2CF2)2OCF2CF2-O-CF2CF2CF2CH2OCH2CH(OH)CH2OH ・・・(A2-1)
1H-NMR(300.4MHz、溶媒:重クロロホルム、基準:TMS) δ(ppm):3.5(8H)、3.7(2H)、3.8(4H)。
19F-NMR(282.7MHz、溶媒:重クロロホルム、基準:CFCl3) δ(ppm):-84.0(28F)、-89.2(28F)、-123.3(4F)、-126.5(24F)。
下式(C-1)で表される化合物(C-1)(ソルベイ社製、フォンブリン(登録商標)Z DOL4000、数平均分子量4,000)を用意した。化合物(C-1)を用いた以外は、例1と同様にして物品を得た。
HO-(CF2O)s(CF2CF2O)t-H ・・・(C-1)
300mLの3つ口丸底フラスコに、tert-ブチルアルコールの50g、カリウムtert-ブトキシドの2.8g、化合物(C-1)の100gを取り入れ、80℃に加熱しながら撹拌し、窒素雰囲気下、グリシドールの3.7gを滴下した。全量滴下した後、5時間撹拌を続けた。その後、氷浴で冷却し、液性が酸性になるまで塩酸水溶液を滴下した。反応終了後、水で1回、飽和食塩水で1回洗浄し、有機相を回収した。回収した液をエバポレータで濃縮した。回収した濃縮液を減圧蒸留し、下式(C-2)で表される化合物(C-2)の99g(収率95%)を得た。化合物(C-2)を用いた以外は、例1と同様にして物品を得た。
HOCH2CH(OH)CH2O-(CF2O)s(CF2CF2O)t-CH2CH(OH)CH2OH ・・・(C-2)
1H-NMR(300.4MHz、溶媒:重クロロホルム、基準:TMS) δ(ppm):3.5(8H)、3.7(2H)、3.8(4H)。
19F-NMR(282.7MHz、溶媒:重クロロホルム、基準:CFCl3) δ(ppm):-84.0(28F)、-89.2(28F)、-123.3(4F)、-126.5(24F)。
例1~4の物品について、最表面(物品の表面のうち表面層を設けた場所)の動摩擦係数、F/Siを測定した。また、例1~4の物品について、含フッ素エーテル化合物と基材上の炭素保護膜との密着性を確認するために、150℃、10mmHgに設定した真空オーブンにそれぞれの物品を1週間保持し、処理後の動摩擦係数、F/Siを測定した。結果を表1に示す。
処理前においては、例3、4は、F/Siが高い数値を示している、すなわち表面層が厚すぎ、潤滑性が不足していることが分かる。一方、例1、2は、F/Siが所望の範囲に入っている、すなわち適した表面層を形成している。
処理後においては、例1、3は、F/Siが所望の範囲を下回っており、さらに、動摩擦係数が高い数値を示している、すなわち処理によって、表面層の一部が消失していることを示している。一方、例2、4は、処理前後で動摩擦系数、F/Siともに変化がないことから、表面層が基材としっかり密着していることを示している。
(例5-1)
下式(10-1)で表される化合物(10-1)、トリエチルアミン、アセトニトリルを撹拌しながら、メシルクロリドを加える。NMRで化合物(10-1)が消費されていることを確認した後に、水で有機相を洗浄し、得られた有機相の溶媒を留去することによって、下式(11-1)で表される化合物(11-1)を得る。
HOCH2CF3 ・・・(10-1)
CH3SO2-OCH2CF3 ・・・(11-1)
例1と同様にして、化合物(A1-1)、すなわち下式(13-1)で表される化合物(13-1)を得る。(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とは一部を除いて交互に配置されている。化合物(13-1)は、含フッ素ポリエーテル化合物(B)として用いてもよい。
HOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2OH ・・・(13-1)
テトラヒドロフラン中、化合物(13-1)と金属ナトリウムとを氷浴で冷却しながら充分に反応させた後に、化合物(11-1)に滴下する。NMRで化合物(11-1)が消費されていることを確認した後に、0.1Nの塩酸で有機相を洗浄し、得られた有機相の溶媒を留去することによって、下式で表される化合物(16-1)、(16-2)および化合物(13-1)の混合物を得る。化合物(16-1)は、含フッ素ポリエーテル化合物(B)として用いてもよい。
HOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2OCH2CF3 ・・・(16-1)
CF3CH2OCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2OCH2CF3 ・・・(16-2)
テトラヒドロフラン中、化合物(13-1)と金属ナトリウムとを充分に反応させた後に、下式(12-1)で表される化合物(12-1)を滴下する。下式で表される化合物(15-1)、(15-2)および化合物(13-1)の混合物を得る。ただし、Phは、フェニル基である。化合物(15-1)、(15-2)は、含フッ素ポリエーテル化合物(B)として用いてもよい。
Ph-I ・・・(12-1)
PhOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2OH ・・・(15-1)
PhOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2OPh ・・・(15-2)
化合物(3-1)、トリエチルアミン、アセトニトリルを撹拌しながら、メシルクロリドを加える。NMRで化合物(3-1)が消費されていることを確認した後に、水で有機相を洗浄し、得られた有機相の溶媒を留去することによって、下式(18-1)で表される化合物(18-1)を得る。
HO-CH2CH2-OH ・・・(3-1)
CH3SO2-O-CH2CH2-O-SO2CH3 ・・・(18-1)
テトラヒドロフラン中、化合物(15-1)と金属ナトリウムとを充分に反応させた後に、化合物(18-1)に滴下する。NMRで化合物(18-1)が消費されていることを確認した後に、0.1Nの塩酸で有機相を洗浄し、得られた有機相の溶媒を留去することによって、下式で表される化合物(19-1)、(A61-1)および化合物(18-1)の混合物を得る。
PhOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2O-CH2CH2-O-SO2CH3 ・・・(19-1)
PhOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2O-CH2CH2-OCH2CF2CF2CF2-[(OCF2CF2)7-(OCF2CF2CF2CF2)4]-O-CF2CF2CF2CH2OPh ・・・(A61-1)
テトラヒドロフラン中、化合物(16-1)と金属ナトリウムとを充分に反応させた後に、化合物(19-1)に滴下する。下式(A62-1)で表される化合物(A62-1)を得る。
PhOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2O-CH2CH2-OCH2CF2CF2CF2-[(OCF2CF2)7-(OCF2CF2CF2CF2)4]-O-CF2CF2CF2CH2OCH2CF3 ・・・(A62-1)
(例6-1)
300mLの三つ口フラスコに環流管を取りつけ、化合物(15-1)の0.3モル、金属ナトリウムの0.33モル、脱水したテトラヒドロフランの100mLを加え、金属ナトリウムが消費されるまで70℃で撹拌を続ける。金属ナトリウウムが消失された後、ホスホニトリルクロリドのシクロトリマーの0.1モルを添加し、同様に70℃で反応させ、NMRで化合物(15-1)の消費を確認し、反応を終了する。反応終了後はアサヒクリンAK-225(旭硝子社製)の50g、0.1N塩酸の50gを添加し、よく撹拌した後に、有機相のみを取り出す。再度、0.1N塩酸の50gを添加し、有機相を洗浄した後に、有機相を取り出し、溶媒を留去して下式(20-1)で表される化合物(20-1)の混合物を得る。
{PhOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2O}m1-P3N3-(Cl)n1 ・・・(20-1)
300mLの三つ口フラスコに環流管を取りつけ、化合物(16-1)の0.3モルと金属ナトリウムの0.33モル、脱水したテトラヒドロフランの100mLを加え、金属ナトリウムが消費されるまで70℃で撹拌を続ける。金属ナトリウウムが消失された後、化合物(20-1)の混合物を添加し、同様に70℃で反応させ、NMRで化合物(20-1)の消費を確認し、反応を終了する。反応終了後はアサヒクリンAK-225(旭硝子社製)の50g、0.1N塩酸の50gを添加し、よく撹拌した後に、有機相のみを取り出す。再度、0.1N塩酸の50gを添加し、有機相を洗浄した後に、有機相を取り出し、溶媒を留去して下式(A63-1)で表される化合物(A63-1)の混合物を得る。
{PhOCH2CF2CF2CF2-O-[(CF2CF2O)7-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2O}m1-P3N3-{OCH2CF2CF2CF2-[(OCF2CF2)7-(OCF2CF2CF2CF2)4]-O-CF2CF2CF2CH2OCH2CF3}n1 ・・・(A63-1)
(例7-1)
下式(21-1)で表される化合物(21-1)(日油社製、ポリセリン(登録商標)DC-1100、(CF2CF2O)単位と(CF2CF2CF2CF2O)単位とはランダムに配置されている。)にフッ化ナトリウムを加え、充分に撹拌し、下式(5-2)で表される化合物(5-2)を滴下した後に、室温で充分に反応させる。化合物(21-1)が消費されたことをNMRで確認した後に、加圧ろ過器でフッ化ナトリウムを除去し、過剰の化合物(5-2)を減圧留去し、下式(22-1)で表される化合物(22-1)を得る。
HO-[(CH2CH2O)15-(CH2CH2CH2CH2O)5]-H ・・・(21-1)
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)F ・・・(5-2)
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)O-[(CH2CH2O)15-(CH2CH2CH2CH2O)5]-C(O)CF(CF3)OCF2(CF3)CFOCF2CF2CF3 ・・・(22-1)
オートクレーブ(ニッケル製)にR-113(CF2ClCFCl2)を投入し、窒素ガスを25℃で1時間吹き込んだ後、20%フッ素ガスを25℃で1時間吹き込む。20%フッ素ガスを同じ流速で吹き込んだ状態で、化合物(22-1)をR-113に希釈して、連続的にフィードする。フィードが完了した時点で、内圧を0.15MPa(ゲージ圧)まで加圧し、25℃から40℃に加熱して撹拌する。NMRで水素原子が残存していないことを確認した後に、窒素ガスを25℃で1時間吹き込んで反応を終了する。得られた反応溶液から溶媒を留去することで、下式(23-1)で表される化合物(23-1)を得る。
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)O-[(CF2CF2O)15-(CF2CF2CF2CF2O)5]-C(O)CF(CF3)OCF2(CF3)CFOCF2CF2CF3 ・・・(23-1)
化合物(23-1)を氷浴で冷却しながら撹拌し、窒素雰囲気下、メタノールをゆっくり滴下した後に、窒素でバブリングしながら12時間撹拌する。NMRで化合物(23-1)の消費を確認した後に、反応溶液から溶媒を留去することで、下式で表される化合物(24-1i)~(24-1iii)の混合物を得る。化合物(24-1i)~(24-1iii)は、含フッ素ポリエーテル化合物(B)として用いてもよい。
CH3OC(O)CF2CF2CF2-O-[(CF2CF2O)15-(CF2CF2CF2CF2O)3]-CF2CF2CF2C(O)OCH3 ・・・(24-1i)
CH3OC(O)CF2-O-[(CF2CF2O)14-(CF2CF2CF2CF2O)4]-CF2CF2CF2C(O)OCH3 ・・・(24-1ii)
CH3OC(O)CF2-O-[(CF2CF2O)13-(CF2CF2CF2CF2O)5]-CF2C(O)OCH3 ・・・(24-1iii)
反応器にエタノール、リチウムクロリド、化合物(24-1i)~(24-1iii)の混合物を入れ、氷浴で冷却しながら撹拌し、窒素雰囲気下、水素化ホウ素ナトリウム粉末をエタノールに分散させたものを滴下する。全量滴下した後、室温までゆっくり昇温し撹拌を続ける。NMRで化合物(24-1i)~(24-1iii)が消費されていることを確認した後に、再び氷浴で冷却し、液性が酸性になるまで0.1Nの塩酸およびアサヒクリンAK-225を添加し、有機相を回収する。再び水で2回洗浄した後に有機相を回収する。回収した有機相から溶媒を留去することで化合物(13a-1i)~(13a-1iii)の混合物を得る。化合物(13a-1i)~(13a-1iii)は、含フッ素ポリエーテル化合物(B)として用いてもよい。
HOCH2CF2CF2CF2-O-[(CF2CF2O)15-(CF2CF2CF2CF2O)3]-CF2CF2CF2CH2OH ・・・(13a-1i)
HOCH2CF2-O-[(CF2CF2O)14-(CF2CF2CF2CF2O)4]-CF2CF2CF2CH2OH ・・・(13a-1ii)
HOCH2CF2-O-[(CF2CF2O)13-(CF2CF2CF2CF2O)5]-CF2CH2OH ・・・(13a-1iii)
(例8-1)
下式(25-1)で表される化合物(25-1)(日油社製、PEG#200)および下式(26-1)で表される化合物(26-1)(日油社製、ユニオール(登録商標)PB-500)を用意する。
HO-(CH2CH2O)4-H ・・・(25-1)
HO-(CH2CH2CH2CH2O)7-H ・・・(26-1)
CH3SO2-O-(CH2CH2O)4-SO2CH3 ・・・(27-1)
CH3SO2-O-(CH2CH2CH2CH2O)7-SO2CH3 ・・・(28-1)
テトラヒドロフラン中、化合物(26-1)と金属ナトリウムとを氷浴で冷却しながら充分に反応させた後に、化合物(27-1)を滴下する。または、テトラヒドロフラン中、化合物(25-1)と金属ナトリウムとを氷浴で冷却しながら充分に反応させた後に、化合物(28-1)を滴下する。このとき、化合物(26-1)または化合物(25-1)のアルコキサイドは、滴下する化合物(27-1)または化合物(28-1)に対して大過剰量存在することが好ましく、化合物(27-1)または化合物(28-1)の滴下速度は反応に対して充分に遅いことが好ましい。NMRで化合物(27-1)または化合物(28-1)が消費されていることを確認した後に、0.1Nの塩酸で有機相を洗浄し、得られた有機相の溶媒を留去することによって、下式(29-1i)で表される化合物(29-1i)または下式(29-1ii)で表される化合物(29-1ii)を得る。
HO-(CH2CH2O)4-(CH2CH2CH2CH2O)7-(CH2CH2O)4-H ・・・(29-1i)
HO-(CH2CH2CH2CH2O)7-(CH2CH2O)4-(CH2CH2CH2CH2O)7-H ・・・(29-1ii)
化合物(29-1i)または化合物(29-1ii)にフッ化ナトリウムを加え、充分に撹拌し、化合物(5-2)を滴下した後に、室温で充分に反応させる。化合物(29-1i)または化合物(29-1ii)が消費されたことをNMRで確認した後に、加圧ろ過器でフッ化ナトリウムを除去し、過剰の化合物(5-2)を減圧留去し、下式(30-1i)で表される化合物(30-1i)または下式(30-1ii)で表される化合物(30-1ii)を得る。
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)F ・・・(5-2)
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)O-(CH2CH2O)4-(CH2CH2CH2CH2O)7-(CH2CH2O)4-C(O)CF(CF3)OCF2(CF3)CFOCF2CF2CF3 ・・・(30-1i)
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)O-(CH2CH2CH2CH2O)7-(CH2CH2O)4-(CH2CH2CH2CH2O)7-C(O)CF(CF3)OCF2(CF3)CFOCF2CF2CF3 ・・・(30-1ii)
オートクレーブ(ニッケル製)にR-113(CF2ClCFCl2)を投入し、窒素ガスを25℃で1時間吹き込んだ後、20%フッ素ガスを25℃で1時間吹き込む。20%フッ素ガスを同じ流速で吹き込んだ状態で、化合物(30-1i)または化合物(30-1ii)をR-113に希釈して、連続的にフィードする。フィードが完了した時点で、内圧を0.15MPa(ゲージ圧)まで加圧し、25℃から40℃に加熱して撹拌する。NMRで水素原子が残存していないことを確認した後に、窒素ガスを25℃で1時間吹き込んで反応を終了する。得られた反応溶液から溶媒を留去することで、下式(31-1i)で表される化合物(31-1i)または下式(31-1ii)で表される化合物(31-1ii)を得る。
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)O-(CF2CF2O)4-(CF2CF2CF2CF2O)7-(CF2CF2O)4-C(O)CF(CF3)OCF2(CF3)CFOCF2CF2CF3 ・・・(31-1i)
CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(O)O-(CF2CF2CF2CF2O)7-(CF2CF2O)4-(CF2CF2CF2CF2O)7-C(O)CF(CF3)OCF2(CF3)CFOCF2CF2CF3 ・・・(31-1ii)
化合物(31-1i)または化合物(31-1ii)を氷浴で冷却しながら撹拌し、窒素雰囲気下、メタノールをゆっくり滴下した後に、窒素でバブリングしながら12時間撹拌する。NMRで化合物(31-1i)または化合物(31-1ii)の消費を確認した後に、反応溶液から溶媒を留去することで、下式(32-1i)で表される化合物(32-1i)または下式(32-1ii)で表される化合物(32-1ii)を得る。化合物(32-1i)、(32-1ii)は、含フッ素ポリエーテル化合物(B)として用いてもよい。
CH3OC(O)CF2-O-(CF2CF2O)3-(CF2CF2CF2CF2O)7-(CF2CF2O)3-CF2C(O)OCH3 ・・・(32-1i)
CH3OC(O)CF2CF2CF2-O-(CF2CF2CF2CF2O)6-(CF2CF2O)4-(CF2CF2CF2CF2O)6-CF2CF2CF2C(O)OCH3 ・・・(32-1ii)
反応器にエタノール、リチウムクロリド、化合物(32-1i)または化合物(32-1ii)を入れ、氷浴で冷却しながら撹拌し、窒素雰囲気下、水素化ホウ素ナトリウム粉末をエタノールに分散させたものを滴下する。全量滴下した後、室温までゆっくり昇温し撹拌を続ける。NMRで化合物(32-1i)または化合物(32-1ii)が消費されていることを確認した後に、再び氷浴で冷却し、液性が酸性になるまで0.1Nの塩酸およびアサヒクリンAK-225を添加し、有機相を回収する。再び水で2回洗浄した後に有機相を回収する。回収した有機層から溶媒を留去することで、下式(13b-1i)で表される化合物(13b-1i)または下式(13b-1ii)で表される化合物(13b-1ii)を得る。化合物(13b-1i)、(13b-1ii)は、含フッ素ポリエーテル化合物(B)として用いてもよい。
HOCH2CF2-O-(CF2CF2O)3-(CF2CF2CF2CF2O)7-(CF2CF2O)3-CF2CH2OH ・・・(13b-1i)
HOCH2CF2CF2CF2-O-(CF2CF2CF2CF2O)6-(CF2CF2O)4-(CF2CF2CF2CF2O)6-CF2CF2CF2CH2OH ・・・(13b-1ii)
なお、2013年8月13日に出願された日本特許出願2013-168103号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (13)
- 下式(A)で表される含フッ素ポリエーテル化合物。
{X-O-[(CF2CF2O)a-(CF2CF2CF2CF2O)b]}m-Y-{[(OCF2CF2)c-(OCF2CF2CF2CF2)d]-O-Z}n ・・・(A)
ただし、
Xは、水酸基、カルボキシ基、エステル基またはアリール基を有する基であり、
Yは、末端にエーテル性酸素原子を有しない、(m+n)価の連結基であり、
Zは、水酸基、カルボキシ基、エステル基およびアリール基を有さず、かつハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)または炭素原子-炭素原子間にエーテル性酸素原子が挿入されたハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)を有する基であり、
mは、1~10の整数であり、
nは、0~10の整数であり、
m+nは、2~20の整数であり、
a、b、c、dは、それぞれ独立に1~100の整数であり、
[(CF2CF2O)a-(CF2CF2CF2CF2O)b]中のa個の(CF2CF2O)単位およびb個の(CF2CF2CF2CF2O)単位の結合順序、および、[(OCF2CF2)c-(OCF2CF2CF2CF2)d]中のc個の(OCF2CF2)単位およびd個の(OCF2CF2CF2CF2)単位の結合順序、は限定されない。 - 数平均分子量が、500~50,000である、請求項1に記載の含フッ素ポリエーテル化合物。
- b/(a+b)が0.2~0.8であり、d/(c+d)が0.2~0.8である、請求項1または2に記載の含フッ素ポリエーテル化合物。
- (OCF2CF2)単位と(OCF2CF2CF2CF2)単位とが交互に配置された構造を有する、請求項1~3のいずれか一項に記載の含フッ素ポリエーテル化合物。
- Xが、HOCH2CH(OH)CH2OCH2CF2CF2CF2-基またはHOCH2CH(OH)CH2OCH2CF2-基である、請求項1~4のいずれか一項に記載の含フッ素ポリエーテル化合物。
- 下式(B)で表される含フッ素ポリエーテル化合物。
X-O-[(CF2CF2O)g-(CF2CF2CF2CF2O)h]-W ・・・(B)
ただし、
Xは、水酸基、カルボキシ基、エステル基またはアリール基を有する基であり、
Wは、水酸基、カルボキシ基、エステル基、アリール基、またはハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)もしくは炭素原子-炭素原子間にエーテル性酸素原子が挿入されたハロアルキル基(ただし、ハロゲン原子はフッ素原子または塩素原子である。)を有する基であり、
g、hは、それぞれ独立に1~200の整数であり、
[(CF2CF2O)g-(CF2CF2CF2CF2O)h]中のg個の(CF2CF2O)単位およびh個の(CF2CF2CF2CF2O)単位の結合順序は限定されない。 - 数平均分子量が、500~50,000である、請求項6に記載の含フッ素ポリエーテル化合物。
- h/(g+h)が0.2~0.8である、請求項6または7に記載の含フッ素ポリエーテル化合物。
- (CF2CF2O)単位と(CF2CF2CF2CF2O)単位とが交互に配置された構造を有する、請求項6~8のいずれか一項に記載の含フッ素ポリエーテル化合物。
- Xが、HOCH2CH(OH)CH2OCH2CF2CF2CF2-基またはHOCH2CH(OH)CH2OCH2CF2-基である、請求項6~9のいずれか一項に記載の含フッ素ポリエーテル化合物。
- 請求項1~10のいずれか一項に記載の含フッ素ポリエーテル化合物を含む、潤滑剤。
- 請求項1~10のいずれか一項に記載の含フッ素ポリエーテル化合物と液状媒体とを含む、液状組成物。
- 基材上に、請求項1~10のいずれか一項に記載の含フッ素ポリエーテル化合物を含む膜を有する、物品。
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