JP6096531B2 - Fluorine-containing alkoxysilane compound, coating agent, and water-repellent film - Google Patents
Fluorine-containing alkoxysilane compound, coating agent, and water-repellent film Download PDFInfo
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- JP6096531B2 JP6096531B2 JP2013034111A JP2013034111A JP6096531B2 JP 6096531 B2 JP6096531 B2 JP 6096531B2 JP 2013034111 A JP2013034111 A JP 2013034111A JP 2013034111 A JP2013034111 A JP 2013034111A JP 6096531 B2 JP6096531 B2 JP 6096531B2
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- JP
- Japan
- Prior art keywords
- fluorine
- alkoxysilane compound
- containing alkoxysilane
- water
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 152
- 229910052731 fluorine Inorganic materials 0.000 title claims description 152
- 239000011737 fluorine Substances 0.000 title claims description 152
- 150000001875 compounds Chemical class 0.000 title claims description 86
- 239000005871 repellent Substances 0.000 title claims description 35
- 239000011248 coating agent Substances 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 11
- 230000002940 repellent Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 description 52
- 239000002904 solvent Substances 0.000 description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- 238000005481 NMR spectroscopy Methods 0.000 description 24
- -1 silane compound Chemical class 0.000 description 23
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 22
- 230000010354 integration Effects 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 21
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 230000002194 synthesizing effect Effects 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000003068 static effect Effects 0.000 description 14
- 239000007810 chemical reaction solvent Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 12
- 238000007654 immersion Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 239000003759 ester based solvent Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000005453 ketone based solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- JTYRBFORUCBNHJ-UHFFFAOYSA-N 1-bromo-1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)Br JTYRBFORUCBNHJ-UHFFFAOYSA-N 0.000 description 4
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229940126208 compound 22 Drugs 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- VQSRKMNBWMHJKY-YTEVENLXSA-N n-[3-[(4ar,7as)-2-amino-6-(5-fluoropyrimidin-2-yl)-4,4a,5,7-tetrahydropyrrolo[3,4-d][1,3]thiazin-7a-yl]-4-fluorophenyl]-5-methoxypyrazine-2-carboxamide Chemical compound C1=NC(OC)=CN=C1C(=O)NC1=CC=C(F)C([C@@]23[C@@H](CN(C2)C=2N=CC(F)=CN=2)CSC(N)=N3)=C1 VQSRKMNBWMHJKY-YTEVENLXSA-N 0.000 description 4
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 4
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 3
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 3
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 3
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 3
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 3
- GRJRKPMIRMSBNK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GRJRKPMIRMSBNK-UHFFFAOYSA-N 0.000 description 3
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- 229940126657 Compound 17 Drugs 0.000 description 3
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- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
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- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 3
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- JDKQTIKEGOOXTJ-UHFFFAOYSA-N pent-4-enoyl chloride Chemical compound ClC(=O)CCC=C JDKQTIKEGOOXTJ-UHFFFAOYSA-N 0.000 description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- SKRWRXWNQFQGRU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane Chemical compound CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SKRWRXWNQFQGRU-UHFFFAOYSA-N 0.000 description 1
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- 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
- SPURMHFLEKVAAS-UHFFFAOYSA-N 1-docosene Chemical compound CCCCCCCCCCCCCCCCCCCCC=C SPURMHFLEKVAAS-UHFFFAOYSA-N 0.000 description 1
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LTTQRUMYWWXCQA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-amine Chemical compound NCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LTTQRUMYWWXCQA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AJIHCPVPJZKWAJ-UHFFFAOYSA-N 8-bromo-1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCBr AJIHCPVPJZKWAJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- AGSFIZDITVHDFK-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.OC.ClC(Cl)Cl AGSFIZDITVHDFK-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- MKRTXPORKIRPDG-UHFFFAOYSA-N diphenylphosphoryl azide Chemical compound C=1C=CC=CC=1P(=O)(N=[N+]=[N-])C1=CC=CC=C1 MKRTXPORKIRPDG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- DKPGJRQAKBRCNH-UHFFFAOYSA-N docos-21-en-1-ol Chemical compound OCCCCCCCCCCCCCCCCCCCCC=C DKPGJRQAKBRCNH-UHFFFAOYSA-N 0.000 description 1
- APBCNLYLPJQPGB-UHFFFAOYSA-N docos-21-enoic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC=C APBCNLYLPJQPGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- LRWGOVMIZOIYFL-UHFFFAOYSA-N oxolan-2-ylidenemethanone Chemical compound O=C=C1CCCO1 LRWGOVMIZOIYFL-UHFFFAOYSA-N 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- LGUZHRODIJCVOC-UHFFFAOYSA-N perfluoroheptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LGUZHRODIJCVOC-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、物質表面を改質するコーティング剤として有用な含フッ素アルコキシシラン化合物、この含フッ素アルコキシシラン化合物を含有するコーティング剤、及びこのコーティング剤を用いて形成される撥水膜に関する。 The present invention relates to a fluorine-containing alkoxysilane compound useful as a coating agent for modifying a material surface, a coating agent containing the fluorine-containing alkoxysilane compound, and a water repellent film formed using the coating agent.
パーフルオロアルキル基（以下、「Ｒｆ基」とも記す）を有する含フッ素アルコキシシラン化合物は、フッ素原子に由来する撥水性及び撥油性を有することから、表面改質用のコーティング剤として広く用いられている。 Fluorine-containing alkoxysilane compounds having a perfluoroalkyl group (hereinafter also referred to as “Rf group”) have water repellency and oil repellency derived from fluorine atoms, and are therefore widely used as coating agents for surface modification. Yes.
このような用途で使用される含フッ素アルコキシシラン化合物は、テロメリゼーションによって合成された、炭素数８以上のＲｆ基を有する化合物が主流であった。しかしながら、炭素数８以上のＲｆ基を有する化合物は、分解又は代謝によって生体内への蓄積性を示すパーフルオロオクタン酸（以下、「ＰＦＯＡ」と記す）を生成することが報告されている（非特許文献１）。このため、ＰＦＯＡは、米国においてパーフルオロオクタンスルホン酸塩（以下、「ＰＦＯＳ」と記す）と同様に環境汚染物質として規制されることが確定している。 As the fluorine-containing alkoxysilane compound used in such applications, compounds having an Rf group having 8 or more carbon atoms synthesized by telomerization have been the mainstream. However, it has been reported that a compound having an Rf group having 8 or more carbon atoms generates perfluorooctanoic acid (hereinafter referred to as “PFOA”) that exhibits accumulation in a living body by decomposition or metabolism (non-non-limiting). Patent Document 1). For this reason, it has been determined that PFOA is regulated as an environmental pollutant in the United States in the same manner as perfluorooctane sulfonate (hereinafter referred to as “PFOS”).
生体蓄積性が少ない化合物として、炭素数７以下のＲｆ基を有する含フッ素アルコキシシラン化合物を挙げることができる（例えば、特許文献１〜４参照）。また、炭素数７以下のＲｆ基を有する含フッ素アルコキシシラン化合物は、上記特許文献に記載されているもの以外にも既に幾つか知られている。 As a compound with little bioaccumulation property, the fluorine-containing alkoxysilane compound which has Rf group of 7 or less carbon atoms can be mentioned (for example, refer patent documents 1-4). Some fluorine-containing alkoxysilane compounds having an Rf group having 7 or less carbon atoms are already known in addition to those described in the above patent documents.
しかしながら、炭素数７以下のＲｆ基を有する従来の含フッ素アルコキシシラン化合物をコーティング剤として使用すると、形成される撥水膜の撥水性や耐久性が不十分であるといった問題があった。 However, when a conventional fluorine-containing alkoxysilane compound having an Rf group having 7 or less carbon atoms is used as a coating agent, there is a problem that the water repellency and durability of the formed water repellent film are insufficient.
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その目的とするところは、環境問題に適合するとともに、パーフルオロアルキル基のフッ素数の減少に伴う撥水性の低下が抑制され、炭素数８以上のパーフルオロアルキル基を有する従来の含フッ素アルコキシシラン化合物を用いた場合と同等又はそれ以上の撥水性及び耐久性を示す撥水膜を形成することが可能な含フッ素アルコキシシラン化合物を提供することにある。また、本発明の目的とするところは、炭素数８以上のパーフルオロアルキル基を有する従来の含フッ素アルコキシシラン化合物を用いた場合と同等又はそれ以上の撥水性及び耐久性を示す撥水膜を提供することにある。 The present invention has been made in view of such problems of the prior art. The object of the present invention is to meet environmental problems and to have water repellency associated with a decrease in the number of fluorine atoms in the perfluoroalkyl group. It is possible to form a water-repellent film exhibiting water repellency and durability equivalent to or higher than when a conventional fluorine-containing alkoxysilane compound having a perfluoroalkyl group having 8 or more carbon atoms is suppressed. The object is to provide a fluorine-containing alkoxysilane compound. Further, the object of the present invention is to provide a water-repellent film having a water repellency and durability equivalent to or higher than that when a conventional fluorine-containing alkoxysilane compound having a perfluoroalkyl group having 8 or more carbon atoms is used. It is to provide.
本発明者らは上記課題を達成すべく鋭意検討した結果、特定構造を有する含フッ素アルコキシシラン化合物を用いることによって、上記課題を達成することが可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved by using a fluorine-containing alkoxysilane compound having a specific structure, and to complete the present invention. It came.
すなわち、本発明によれば、以下に示す含フッ素アルコキシシラン化合物が提供される。
［１］下記一般式（１）で表される含フッ素アルコキシシラン化合物。
Ｒｆ−Ａ−Ｂ−ＳｉＸ3 ・・・（１）
（前記一般式（１）中、Ｒｆは炭素数３〜６のパーフルオロアルキル基を示し、Ａは−ＣＯＯ−、−Ｏ−、−Ｓ−、又は−ＣＯ−Ｓ−を示し、Ｂは−（ＣＨ2）m−（ｍ＝５〜２０）を示し、Ｘは−ＯＣnＨ2n+1（ｎ＝１〜４）を示し、３つのＸは互いに同一でも異なっていてもよい）
［２］前記一般式（１）中、Ａが−ＣＯＯ−である前記［１］に記載の含フッ素アルコキシシラン化合物。
That is, according to the present invention, the following fluorine-containing alkoxysilane compound is provided.
[1] A fluorine-containing alkoxysilane compound represented by the following general formula (1).
Rf-A-B-SiX 3 (1)
(In the general formula (1), Rf represents a perfluoroalkyl group of 3-6 carbon atoms, A is -COO -, - O -, - S-, or -CO-S- are shown, the B - (CH 2 ) m — (m = 5 to 20), X represents —OC n H 2n + 1 (n = 1 to 4), and three Xs may be the same or different from each other)
[2] The fluorine-containing alkoxysilane compound according to [1], wherein A is —COO— in the general formula (1).
また、本発明によれば、以下に示すコーティング剤が提供される。
［３］前記［１］又は［２］に記載の含フッ素アルコキシシラン化合物を含有するコーティング剤。
Moreover, according to this invention, the coating agent shown below is provided.
[3] A coating agent containing the fluorine-containing alkoxysilane compound according to [1] or [2].
さらに、本発明によれば、以下に示す撥水膜が提供される。
［４］前記［３］に記載のコーティング剤を用いて形成される撥水膜。
Furthermore, according to the present invention, the following water-repellent film is provided.
[4] A water repellent film formed using the coating agent according to [3].
本発明の含フッ素アルコキシシラン化合物を用いれば、パーフルオロアルキル基のフッ素数の減少に伴う撥水性の低下が抑制され、炭素数８以上のパーフルオロアルキル基を有する従来の含フッ素アルコキシシラン化合物を用いた場合と同等又はそれ以上の撥水性及び耐久性を示す撥水膜を形成することができる。また、本発明の含フッ素アルコキシシラン化合物は、パーフルオロアルキル基の炭素数が８に満たないため、環境問題にも適合している。そして、本発明の含フッ素アルコキシシラン化合物をコーティング剤として利用することで、高い撥水性と耐久性を示す撥水膜を提供することができる。 When the fluorine-containing alkoxysilane compound of the present invention is used, a decrease in water repellency associated with a decrease in the number of fluorine atoms in the perfluoroalkyl group is suppressed, and a conventional fluorine-containing alkoxysilane compound having a perfluoroalkyl group having 8 or more carbon atoms is obtained. It is possible to form a water repellent film exhibiting water repellency and durability equivalent to or higher than when used. Further, the fluorine-containing alkoxysilane compound of the present invention is suitable for environmental problems because the perfluoroalkyl group has less than 8 carbon atoms. And the water-repellent film which shows high water repellency and durability can be provided by utilizing the fluorine-containing alkoxysilane compound of this invention as a coating agent.
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。 Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.
（含フッ素アルコキシシラン化合物）
本発明の含フッ素アルコキシシラン化合物は、下記一般式（１）で表される化合物である。
Ｒｆ−Ａ−Ｂ−ＳｉＸ3 ・・・（１）
（前記一般式（１）中、Ｒｆは炭素数３〜６のパーフルオロアルキル基を示し、Ａは−ＣＯＯ−、−Ｏ−、−Ｓ−、又は−ＣＯ−Ｓ−を示し、Ｂは−（ＣＨ2）m−（ｍ＝５〜２０）を示し、Ｘは−ＯＣnＨ2n+1（ｎ＝１〜４）を示し、３つのＸは互いに同一でも異なっていてもよい）
(Fluorine-containing alkoxysilane compound)
The fluorine-containing alkoxysilane compound of the present invention is a compound represented by the following general formula (1).
Rf-A-B-SiX 3 (1)
(In the general formula (1), Rf represents a perfluoroalkyl group of 3-6 carbon atoms, A is -COO -, - O -, - S-, or -CO-S- are shown, the B - (CH 2 ) m — (m = 5 to 20), X represents —OC n H 2n + 1 (n = 1 to 4), and three Xs may be the same or different from each other)
一般式（１）中のＲｆは、炭素数３〜６のパーフルオロアルキル基である。Ｒｆ基の炭素数を上記範囲とすることで、環境問題に適合した化合物でありながらも、良好な撥水性を示す撥水膜を形成することができる。また、本発明の含フッ素アルコキシシラン化合物は、一般式（１）中のＡ基がＲｆ基と直接結合した構造を有する。このような構造とすることで、形成される撥水膜の耐久性が飛躍的に向上する。形成される撥水膜の耐久性がこのように向上する理由については明らかではないが、Ａ基をＲｆ基と直接結合させたことでＡ基が水の求核攻撃を受けにくくなり、加水分解しにくくなったためであると推測される。 Rf in Formula (1) is a perfluoroalkyl group of 3-6 carbon atoms. By setting the number of carbon atoms in the Rf group within the above range, it is possible to form a water repellent film exhibiting good water repellency while being a compound suitable for environmental problems. The fluorine-containing alkoxysilane compound of the present invention has a structure in which the A group in the general formula (1) is directly bonded to the Rf group. By adopting such a structure, the durability of the formed water repellent film is dramatically improved. The reason why the durability of the formed water-repellent film is improved is not clear, but the A group becomes less susceptible to nucleophilic attack of water by directly bonding the A group to the Rf group, resulting in hydrolysis. This is presumably because it became difficult to do.
一般式（１）中のＡは、合成の容易さ及び形成される撥水膜の耐久性を向上させる観点から、−ＣＯＯ−、−Ｏ−、−Ｓ−、及び−ＣＯ−Ｓ−から選択される連結基である。一般式（１）中のＡが上記以外の連結基、例えば、−ＮＨＣＯ−、−ＮＨＣＯＯ−、又は−ＮＨＣＯＮＨ−等であると親水性が増大してしまい、加水分解を受けやすくなって撥水膜の耐久性が低下する場合がある。なお、一般式（１）中のＡは−ＣＯＯ−であることが、他の連結基に比して凝集エネルギーが高くなり、撥水膜の耐久性が向上するためにより好ましい。 A in the general formula (1) is selected from —COO—, —O—, —S—, and —CO—S— from the viewpoint of improving the ease of synthesis and the durability of the formed water-repellent film. A linking group. If A in the general formula (1) is a linking group other than those described above, for example, —NHCO—, —NHCOO—, or —NHCONH—, etc., the hydrophilicity will increase, and it will be susceptible to hydrolysis and water repellency. The durability of the membrane may be reduced. In addition, it is more preferable that A in the general formula (1) is —COO— because the cohesive energy is higher than that of other linking groups and the durability of the water-repellent film is improved.
一般式（１）中のＢは、炭素数５〜２０（ｍ＝５〜２０）のアルキレンであり、炭素数５〜１０（ｍ＝５〜１０）のアルキレンであることがさらに好ましい。Ｂの炭素数を上記範囲とすることで含フッ素アルコキシシラン化合物の疎水性が強まり、Ｒｆ基の撥水性を補うのに効果的となる。なお、Ｂの炭素数が５未満（４以下）であると含フッ素アルコキシシラン化合物の疎水性が弱まってしまい、Ｒｆ基の撥水性を補うほどの効果が出ない。一方、Ｂの炭素数が２０を超える（２１以上）であると、アルコキシシランがシラノールへと加水分解しにくくなる場合がある。 B in the general formula (1) is alkylene having 5 to 20 carbon atoms (m = 5 to 20), and more preferably alkylene having 5 to 10 carbon atoms (m = 5 to 10). By setting the carbon number of B within the above range, the hydrophobicity of the fluorine-containing alkoxysilane compound is enhanced, and it is effective to supplement the water repellency of the Rf group. In addition, when the carbon number of B is less than 5 (4 or less), the hydrophobicity of the fluorine-containing alkoxysilane compound is weakened, and the effect of supplementing the water repellency of the Rf group does not appear. On the other hand, if the carbon number of B exceeds 20 (21 or more), the alkoxysilane may be difficult to hydrolyze into silanol.
一般式（１）中のＸは、シラン化合物等に従来用いられているアルコキシ基であればよいが、具体的には−ＯＣnＨ2n+1（ｎ＝１〜４）である。一般式（１）中のＸを−ＯＣnＨ2n+1（ｎ＝１〜４）とすることで、アルコキシシランのシラノールへの加水分解が容易となるために好ましい。なお、一般式（１）中の３つのＸは、互いに同一でも異なっていてもよい。 X in the general formula (1) may be an alkoxy group conventionally used for a silane compound or the like, and specifically is —OC n H 2n + 1 (n = 1 to 4). It is preferable to set X in the general formula (1) to -OC n H 2n + 1 (n = 1 to 4) because hydrolysis of alkoxysilane to silanol becomes easy. In addition, three X in General formula (1) may mutually be same or different.
（含フッ素アルコキシシラン化合物の合成方法）
本発明の含フッ素アルコキシシラン化合物は、従来公知の方法で合成することができる。例えば、一般式（１）中のＡが−ＣＯＯ−である含フッ素アルコキシシラン化合物については、以下に示すスキームに従って合成することができる。
(Method for synthesizing fluorine-containing alkoxysilane compound)
The fluorine-containing alkoxysilane compound of the present invention can be synthesized by a conventionally known method. For example, the fluorine-containing alkoxysilane compound in which A in the general formula (1) is —COO— can be synthesized according to the scheme shown below.
また、一般式（１）中のＡが−Ｏ−である含フッ素アルコキシシラン化合物については、以下に示すスキームに従って合成することができる。 Moreover, about the fluorine-containing alkoxysilane compound whose A in General formula (1) is -O-, it is compoundable according to the scheme shown below.
さらに、一般式（１）中のＡが−Ｓ−である含フッ素アルコキシシラン化合物については、以下に示すスキームに従って合成することができる。 Furthermore, about the fluorine-containing alkoxysilane compound whose A in General formula (1) is -S-, it is compoundable according to the scheme shown below.
なお、一般式（１）中のＡが−ＣＯ−Ｓ−である含フッ素アルコキシシラン化合物については、以下に示すスキームに従って合成することができる。 In addition, about the fluorine-containing alkoxysilane compound whose A in General formula (1) is -CO-S-, it is compoundable according to the scheme shown below.
（反応溶媒）
本発明の含フッ素アルコキシシラン化合物の合成するための反応は、溶媒中又は無溶媒下で実施することができる。溶媒中で合成する際に用いる反応溶媒としては、反応に影響しにくく、原料の溶解性が適度なものを選択すればよい。一般式（１）中のＡが−ＣＯＯ−である含フッ素アルコキシシラン化合物を合成する場合に用いる反応溶媒の具体例としては、ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒；アセトン、メチルイソブチルケトン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；ヘキサン、ヘプタン、トルエン、キシレン等の炭化水素系溶媒；ジクロロメタン、クロロホルム等のハロゲン系溶媒等を挙げることができる。また、原料のアルコールを反応系に過剰量添加し、これを反応溶媒として用いることもできる。
(Reaction solvent)
The reaction for synthesizing the fluorine-containing alkoxysilane compound of the present invention can be carried out in a solvent or under no solvent. As a reaction solvent used when synthesizing in a solvent, a reaction solvent which does not easily affect the reaction and has an appropriate solubility of raw materials may be selected. Specific examples of the reaction solvent used when synthesizing the fluorine-containing alkoxysilane compound in which A in the general formula (1) is —COO— include ether solvents such as diethyl ether and tetrahydrofuran; acetone, methyl isobutyl ketone and the like. Examples include ketone solvents; ester solvents such as ethyl acetate and butyl acetate; hydrocarbon solvents such as hexane, heptane, toluene, and xylene; halogen solvents such as dichloromethane and chloroform. Further, an excessive amount of raw material alcohol can be added to the reaction system and used as a reaction solvent.
一般式（１）中のＡが−Ｏ−及び−Ｓ−である含フッ素アルコキシシラン化合物を合成する場合には、第１ステップのエーテル化反応又はスルフィド化反応において、例えば、ジメチルスルホキシド、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド等を使用することができる。また、第２ステップのヒドロシリル化反応においては、例えば、ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒；アセトン、メチルイソブチルケトン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；ヘキサン、ヘプタン、トルエン、キシレン等の炭化水素系溶媒；ジクロロメタン、クロロホルム等のハロゲン系溶媒；メタノール、エタノール等のアルコール等を使用することができる。 When synthesizing a fluorine-containing alkoxysilane compound in which A in the general formula (1) is —O— or —S—, in the etherification reaction or sulfidation reaction in the first step, for example, dimethyl sulfoxide, acetonitrile, N, N-dimethylformamide and the like can be used. In the second step hydrosilylation reaction, for example, ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; hexane, heptane, Hydrocarbon solvents such as toluene and xylene; halogen solvents such as dichloromethane and chloroform; alcohols such as methanol and ethanol can be used.
一般式（１）中のＡが−ＣＯ−Ｓ−である含フッ素アルコキシシラン化合物を合成する場合には、第１ステップのチオエステル化反応において、例えば、ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒；アセトン、メチルイソブチルケトン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；ヘキサン、ヘプタン、トルエン、キシレン等の炭化水素系溶媒；ジクロロメタン、クロロホルム等のハロゲン系溶媒；トリエチルアミン、ピリジン等のアミン系溶媒等を使用することができる。また、原料のチオールを反応系に過剰量添加し、これを反応溶媒として用いることもできる。
第２ステップのヒドロシリル化反応においては、例えば、ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒；アセトン、メチルイソブチルケトン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；ヘキサン、ヘプタン、トルエン、キシレン等の炭化水素系溶媒；ジクロロメタン、クロロホルム等のハロゲン系溶媒；メタノール、エタノール等のアルコール等を使用することができる。なお、これらの反応溶媒の使用量は特に限定されない。
When synthesizing a fluorine-containing alkoxysilane compound in which A in the general formula (1) is -CO-S-, in the first step thioesterification reaction, for example, an ether solvent such as diethyl ether or tetrahydrofuran; acetone Ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; hydrocarbon solvents such as hexane, heptane, toluene and xylene; halogen solvents such as dichloromethane and chloroform; amines such as triethylamine and pyridine A system solvent or the like can be used. Further, an excessive amount of raw material thiol can be added to the reaction system, and this can be used as a reaction solvent.
In the second step hydrosilylation reaction, for example, ether solvents such as diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; hexane, heptane, toluene, Hydrocarbon solvents such as xylene; halogen solvents such as dichloromethane and chloroform; alcohols such as methanol and ethanol can be used. In addition, the usage-amount of these reaction solvents is not specifically limited.
（触媒）
本発明の含フッ素アルコキシシラン化合物を合成する際には、従来公知の触媒を使用することができる。例えば、前述のヒドロシリル化反応においては、Ｓｐｅｉｅｒ触媒、及びＫａｒｓｔｅｄｔ触媒等を使用することができる。
(catalyst)
In synthesizing the fluorine-containing alkoxysilane compound of the present invention, a conventionally known catalyst can be used. For example, in the aforementioned hydrosilylation reaction, a Speier catalyst, a Karstedt catalyst, or the like can be used.
（反応温度）
本発明の含フッ素アルコキシシラン化合物を合成する際の反応温度は特に限定されない。反応の進行具合、使用する試薬、又は反応溶媒の沸点等によって適宜設定すればよい。
(Reaction temperature)
The reaction temperature for synthesizing the fluorine-containing alkoxysilane compound of the present invention is not particularly limited. What is necessary is just to set suitably according to the progress of reaction, the reagent to be used, the boiling point of the reaction solvent, etc.
（反応雰囲気）
本発明の含フッ素アルコキシシラン化合物を合成する際の反応雰囲気は特に限定されない。具体的には、窒素やアルゴン等の不活性ガス雰囲気下、又は空気等の雰囲気化で反応させることができる。
(Reaction atmosphere)
The reaction atmosphere when synthesizing the fluorine-containing alkoxysilane compound of the present invention is not particularly limited. Specifically, the reaction can be performed in an inert gas atmosphere such as nitrogen or argon, or in an atmosphere such as air.
合成した含フッ素アルコキシシラン化合物の分子構造は、ＮＭＲ（核磁気共鳴装置）やＩＲ（赤外分光光度計）等を用いて同定することができる。 The molecular structure of the synthesized fluorine-containing alkoxysilane compound can be identified using NMR (nuclear magnetic resonance apparatus), IR (infrared spectrophotometer) or the like.
本発明の含フッ素アルコキシシラン化合物の分子構造のうち、代表的なものを以下に例示する。ただし、本発明の含フッ素アルコキシシラン化合物は以下に示す分子構造を有するものに限定されない。
含フッ素アルコキシシラン化合物１：Ｃ6Ｆ13−ＣＯＯ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3
含フッ素アルコキシシラン化合物２：Ｃ6Ｆ13−ＣＯＯ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ3）3
含フッ素アルコキシシラン化合物３：Ｃ3Ｆ7−ＣＯＯ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ3）3
含フッ素アルコキシシラン化合物４：Ｃ3Ｆ7−ＣＯＯ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3
含フッ素アルコキシシラン化合物５：Ｃ6Ｆ13−ＣＯＯ−（ＣＨ2）20−Ｓｉ−（ＯＣＨ2ＣＨ3）3
含フッ素アルコキシシラン化合物６：Ｃ6Ｆ13−ＣＯＯ−（ＣＨ2）5−Ｓｉ−（ＯＣＨ2ＣＨ3）3
含フッ素アルコキシシラン化合物７：Ｃ6Ｆ13−Ｏ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3
含フッ素アルコキシシラン化合物８：Ｃ6Ｆ13−Ｓ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3
含フッ素アルコキシシラン化合物９：Ｃ6Ｆ13−Ｃ（＝Ｏ）Ｓ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3
Typical examples of the molecular structure of the fluorine-containing alkoxysilane compound of the present invention are shown below. However, the fluorine-containing alkoxysilane compound of the present invention is not limited to those having the molecular structure shown below.
Fluorine-containing alkoxysilane compound 1: C 6 F 13 -COO- ( CH 2) 10 -Si- (OCH 2 CH 3) 3
Fluorine-containing alkoxysilane compound 2: C 6 F 13 -COO- ( CH 2) 10 -Si- (OCH 3) 3
Fluorine-containing alkoxysilane compound 3: C 3 F 7 -COO- ( CH 2) 10 -Si- (OCH 3) 3
Fluorine-containing alkoxysilane compound 4: C 3 F 7 -COO- ( CH 2) 10 -Si- (OCH 2 CH 3) 3
Fluorine-containing alkoxysilane compound 5: C 6 F 13 -COO- ( CH 2) 20 -Si- (OCH 2 CH 3) 3
Fluorine-containing alkoxysilane compound 6: C 6 F 13 -COO- ( CH 2) 5 -Si- (OCH 2 CH 3) 3
Fluorine-containing alkoxysilane compound 7: C 6 F 13 -O- ( CH 2) 10 -Si- (OCH 2 CH 3) 3
Fluorine-containing alkoxysilane compound 8: C 6 F 13 -S- ( CH 2) 10 -Si- (OCH 2 CH 3) 3
Fluorine-containing alkoxysilane compound 9: C 6 F 13 -C ( = O) S- (CH 2) 10 -Si- (OCH 2 CH 3) 3
（撥水膜）
上述の含フッ素アルコキシシラン化合物をコーティング剤として用いることで、本発明の撥水膜を形成することができる。より具体的には、本発明の撥水膜は、以下に示す（ｉ）〜（ｉｉｉ）をコーティング剤として使用し、基材等の表面上に塗布して成膜することで製造することができる。
（ｉ）含フッ素アルコキシシラン化合物のみ
（ｉｉ）含フッ素アルコキシシラン化合物の一部が縮合されたもの
（ｉｉｉ）含フッ素アルコキシシラン化合物と、メチルトリエトキシシランやテトラエトキシシラン等の従来使用されているシランカップリング剤とを混合して得られる、含フッ素アルコキシシラン化合物の一部が縮合された混合物
(Water repellent film)
By using the above-mentioned fluorine-containing alkoxysilane compound as a coating agent, the water-repellent film of the present invention can be formed. More specifically, the water-repellent film of the present invention can be produced by using (i) to (iii) shown below as a coating agent and applying the film on a surface of a substrate or the like to form a film. it can.
(I) Fluorine-containing alkoxysilane compound only (ii) A part of the fluorine-containing alkoxysilane compound is condensed (iii) Fluorine-containing alkoxysilane compound and methyltriethoxysilane, tetraethoxysilane, etc. are conventionally used A mixture obtained by mixing a silane coupling agent with a part of a fluorine-containing alkoxysilane compound condensed
コーティング剤として使用される上記（ｉｉ）、（ｉｉｉ）は、アルコキシシランが加水分解された後に脱水縮合して得られる、Ｓｉ−Ｏ−Ｓｉ結合で一部が繋がった縮合物である。 The above (ii) and (iii) used as a coating agent are condensates partially linked by Si—O—Si bonds obtained by dehydration condensation after hydrolysis of alkoxysilane.
（縮合物を合成する際の反応溶媒）
上記の縮合物を合成する際に用いられる反応溶媒は特に限定されない。反応溶媒の具体例としては、メタノール、エタノール、プロパノール、ブタノール等のアルコール溶媒等を挙げることができる。なお、反応溶媒の使用量は特に限定されない。
(Reaction solvent for synthesizing the condensate)
The reaction solvent used when synthesizing the condensate is not particularly limited. Specific examples of the reaction solvent include alcohol solvents such as methanol, ethanol, propanol and butanol. In addition, the usage-amount of the reaction solvent is not specifically limited.
（縮合物を合成する際の触媒）
上記の縮合物を合成する際には触媒を用いることができる。触媒の具体例としては、ギ酸、酢酸等の有機酸；塩酸、硫酸等の無機酸；ジブチル錫ジメトキシド、テトラ−ｎ−ブチルチタネート等の有機金属等を挙げることができる。
(Catalyst for synthesizing condensate)
A catalyst can be used when synthesizing the condensate. Specific examples of the catalyst include organic acids such as formic acid and acetic acid; inorganic acids such as hydrochloric acid and sulfuric acid; organic metals such as dibutyltin dimethoxide and tetra-n-butyl titanate.
（縮合物を合成する際の反応温度）
上記の縮合物を合成する際の反応温度は特に限定されない。反応の進行具合、使用する試薬、又は反応溶媒の沸点等によって適宜設定すればよい。
(Reaction temperature when synthesizing the condensate)
The reaction temperature at the time of synthesizing the condensate is not particularly limited. What is necessary is just to set suitably according to the progress of reaction, the reagent to be used, the boiling point of the reaction solvent, etc.
（縮合物を合成する際の反応雰囲気）
上記の縮合物を合成する際の反応雰囲気は特に限定されない。具体的には、窒素やアルゴン等の不活性ガス雰囲気下、又は空気等の雰囲気化で反応させることができる。
(Reaction atmosphere when synthesizing condensate)
The reaction atmosphere when synthesizing the condensate is not particularly limited. Specifically, the reaction can be performed in an inert gas atmosphere such as nitrogen or argon, or in an atmosphere such as air.
（コーティング剤の希釈溶媒）
上記のコーティング剤はそのまま用いることもできるが、希釈溶媒で希釈したものを使用してもよい。希釈溶媒としては、例えば、１，１，１，２，２，３，３，４，４，５，５，６，６−トリデカフルオロオクタン、パーフルオロヘプタン等の含フッ素脂肪族炭化水素系溶媒；ベンゾトリフロライド、ｍ−キシレンヘキサンフロライド等の含フッ素芳香族炭化水素系溶媒；ＨＦＥ−３４７ｐｃ−ｆ、ＨＦＥ−５６９ｓｆ等の含フッ素エーテル系溶媒；ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒；アセトン、メチルイソブチルケトン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；ヘキサン、ヘプタン、トルエン、キシレン等の炭化水素系溶媒；ジクロロメタン、クロロホルム等のハロゲン系溶媒；メタノール、エタノール等のアルコール等を使用することができる。これらの希釈溶媒のなかでも、フッ素系溶媒、又はフッ素系溶媒と非フッ素系溶媒の混合溶媒は、含フッ素アルコキシシラン化合物を容易に溶解することができるために好ましい。なお、希釈溶媒の使用量は、使用状況に応じて適宜設定すればよい。
(Diluting solvent for coating agent)
Although the above coating agent can be used as it is, it may be diluted with a diluent solvent. Examples of the diluting solvent include fluorine-containing aliphatic hydrocarbons such as 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane and perfluoroheptane. Solvent; Fluorine-containing aromatic hydrocarbon solvent such as benzotrifluoride and m-xylenehexane fluoride; Fluorine-containing ether solvent such as HFE-347pc-f and HFE-569sf; Ether solvent such as diethyl ether and tetrahydrofuran Ketone solvents such as acetone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; hydrocarbon solvents such as hexane, heptane, toluene and xylene; halogen solvents such as dichloromethane and chloroform; methanol, ethanol, etc. Can be used. Among these diluting solvents, a fluorinated solvent or a mixed solvent of a fluorinated solvent and a non-fluorinated solvent is preferable because the fluorinated alkoxysilane compound can be easily dissolved. In addition, what is necessary is just to set the usage-amount of a dilution solvent suitably according to a use condition.
本発明の撥水膜は、上記コーティング剤を基材の表面上に塗布した後、室温条件下又は加熱条件下で乾燥すること等によって形成することができる。 The water repellent film of the present invention can be formed by applying the coating agent on the surface of the substrate and then drying it under room temperature conditions or heating conditions.
（基材）
基材としては、例えば、無機系反射防止膜（ＳｉＯ2）、ガラス、ハードコート膜、陶磁器、金属等を使用することができる。
(Base material)
As the substrate, for example, an inorganic antireflection film (SiO 2 ), glass, a hard coat film, ceramics, metal or the like can be used.
（塗布方法）
塗布方法は特に限定されないが、例えば、ディップ法、スピンコート法、バーコート法、スプレー法、刷毛を用いた塗布方法等の方法を利用することができる。
(Application method)
The application method is not particularly limited, and for example, a dipping method, a spin coating method, a bar coating method, a spray method, a coating method using a brush, or the like can be used.
（乾燥方法）
乾燥温度は、溶媒の発火点や引火点、基材の耐熱温度等により適宜設定すればよい。具体的には、室温（２５℃）以上３００℃以下とすることが好ましく、４０℃以上２５０℃以下とすることがさらに好ましく、５０℃以上１５０℃以下とすることが特に好ましい。また、乾燥時間は、溶媒が十分に除去され、形成される撥水膜の表面が硬化する時間とすればよい。
(Drying method)
What is necessary is just to set a drying temperature suitably by the ignition point of a solvent, flash point, the heat-resistant temperature of a base material, etc. Specifically, the temperature is preferably from room temperature (25 ° C.) to 300 ° C., more preferably from 40 ° C. to 250 ° C., and particularly preferably from 50 ° C. to 150 ° C. The drying time may be a time for sufficiently removing the solvent and curing the surface of the formed water-repellent film.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載における「部」及び「％」は、特に断らない限り質量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “part” and “%” are based on mass unless otherwise specified.
（１）含フッ素アルコキシシラン化合物の合成
［実施例１］
反応容器中に、９−デセン−１−オール１．００部及びトリデカフルオロヘプタン酸２．８０部を投入し、撹拌しながら１００℃で５時間加熱した。反応液を水酸化ナトリウム水溶液とクロロホルムで分液した後、有機層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．３９部を８０℃で２時間反応させて含フッ素アルコキシシラン化合物１を得た。得られた含フッ素アルコキシシラン化合物１を1Ｈ−ＮＭＲ（商品名「ＥＣＡ４００」、日本電子社製）で測定したところ、δ０．６０ｐｐｍ（２Ｈ，ｔ）、δ１．１５−１．４５ｐｐｍ（２３Ｈ，ｍ）、δ１．７２ｐｐｍ（２Ｈ，ｍ）、δ３．７５−３．９０ｐｐｍ（６Ｈ，ｍ）、δ４．３５ｐｐｍ（２Ｈ，ｔ）にシグナルが観測された。また、19Ｆ−ＮＭＲ（商品名「ＥＣＡ４００」、日本電子社製）による測定から、フッ素の積分比が１３であることを確認した。さらに、含フッ素アルコキシシラン化合物１をＦＴ−ＩＲ（商品名「Ｐｒｅｓｔｉｇｅ２１」、島津製作所社製）で測定したところ、１７８２ｃｍ-1にエステル、１０８０ｃｍ-1、１１０５ｃｍ-1にエトキシシリルによる吸収が観測された。これらの結果から帰属される含フッ素アルコキシシラン化合物１の構造を表１に示す。
(1) Synthesis of fluorine-containing alkoxysilane compound [Example 1]
Into the reaction vessel, 1.00 part of 9-decen-1-ol and 2.80 parts of tridecafluoroheptanoic acid were added and heated at 100 ° C. for 5 hours with stirring. The reaction solution was partitioned between an aqueous sodium hydroxide solution and chloroform, and then the organic layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.39 part of triethoxysilane were reacted at 80 ° C. for 2 hours to obtain a fluorine-containing alkoxysilane compound 1. When the obtained fluorine-containing alkoxysilane compound 1 was measured by 1 H-NMR (trade name “ECA400”, manufactured by JEOL Ltd.), δ0.60 ppm (2H, t), δ1.15-1.45 ppm (23H, m), δ 1.72 ppm (2H, m), δ 3.75-3.90 ppm (6H, m), and δ 4.35 ppm (2H, t) were observed. Moreover, it was confirmed that the integration ratio of fluorine was 13 from the measurement by 19 F-NMR (trade name “ECA400”, manufactured by JEOL Ltd.). Furthermore, the fluorine-containing alkoxysilane compound 1 FT-IR (trade name "Prestige21", manufactured by Shimadzu Corp.) was measured, the ester 1782cm -1, 1080cm -1, absorption by triethoxysilyl to 1105cm -1 was observed It was. Table 1 shows the structure of the fluorine-containing alkoxysilane compound 1 attributed to these results.
［実施例２］
トリエトキシシランをトリメトキシシラン０．２９部に変更したこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物２を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物２をＮＭＲで測定し、−（ＣＨ2）10−Ｓｉ−（ＯＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、メトキシシリルによる吸収を観測した。含フッ素アルコキシシラン化合物２の構造を表１に示す。
[Example 2]
A fluorine-containing alkoxysilane compound 2 was obtained in the same manner as in Example 1 except that triethoxysilane was changed to 0.29 part of trimethoxysilane. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 2 was measured by NMR, and the proton signal and fluorine integration ratio due to — (CH 2 ) 10 —Si— (OCH 3 ) 3 were confirmed. Absorption by ester and methoxysilyl was observed by FT-IR. The structure of the fluorine-containing alkoxysilane compound 2 is shown in Table 1.
［実施例３］
トリデカフルオロヘプタン酸をヘプタフルオロ酪酸１．６４部に変更するとともに、トリエトキシシランをトリメトキシシラン０．４２部に変更したこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物３を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物３をＮＭＲで測定し、−（ＣＨ2）10−Ｓｉ−（ＯＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、メトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物３の構造を表１に示す。
[Example 3]
Fluorine-containing alkoxysilane compound as described in Example 1 except that tridecafluoroheptanoic acid was changed to 1.64 parts heptafluorobutyric acid and triethoxysilane was changed to 0.42 parts trimethoxysilane . 3 was obtained. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 3 was measured by NMR, and the proton signal and fluorine integration ratio due to — (CH 2 ) 10 —Si— (OCH 3 ) 3 were confirmed. Absorption by ester and methoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 3 is shown in Table 1.
［実施例４］
トリデカフルオロヘプタン酸をヘプタフルオロ酪酸１．６４部に変更するとともに、トリエトキシシランを０．５６部用いたこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物４を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物４をＮＭＲで測定し、−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物４の構造を表１に示す。
[Example 4]
A fluorine-containing alkoxysilane compound 4 was obtained in the same manner as in Example 1 except that tridecafluoroheptanoic acid was changed to 1.64 parts of heptafluorobutyric acid and 0.56 parts of triethoxysilane was used . . In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 4 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 10 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Absorption by ester and ethoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 4 is shown in Table 1.
［実施例５］
エチレンオキシドと１８−ブロモ−１−オクタデセンを使用し、非特許文献（Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ，Ｃｏｌｌ．Ｖｏｌ．１，ｐ．３０６（１９４１）；Ｖｏｌ．６，ｐ．５４（１９２６））の記載を参考にして１９−エイコセン−１−オールを合成した。次いで、９−デセン−１−オールを１９−エイコセン−１−オール１．００部に変更するとともに、トリデカフルオロヘプタン酸を１．４７部及びトリエトキシシランを０．３１部用いたこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物５を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物５をＮＭＲで測定し、−（ＣＨ2）20−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物５の構造を表１に示す。
[Example 5]
Using ethylene oxide and 18-bromo-1-octadecene, with reference to the description of non-patent literature (Organic Synthesis, Coll. Vol. 1, p. 306 (1941); Vol. 6, p. 54 (1926)) 19-eicosen-1-ol was synthesized. Subsequently, 9-decene-1-ol was changed to 1.00 parts of 19-eicosen-1-ol, and 1.47 parts of tridecafluoroheptanoic acid and 0.31 parts of triethoxysilane were used. In the same manner as in Example 1, the fluorine-containing alkoxysilane compound 5 was obtained. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 5 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 20 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Absorption by ester and ethoxysilyl was observed by FT-IR. Table 1 shows the structure of the resulting fluorine-containing alkoxysilane compound 5.
［実施例６］
９−デセン−１−オールを４−ペンテン−１−オール１．００部に変更するとともに、トリデカフルオロヘプタン酸を４．３６部及びトリエトキシシランを０．４４部用いたこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物６を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物６をＮＭＲで測定し、−（ＣＨ2）5−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物６の構造を表１に示す。
[Example 6]
Except for changing 9-decen-1-ol to 1.00 parts of 4- penten -1-ol and using 4.36 parts of tridecafluoroheptanoic acid and 0.44 parts of triethoxysilane. In the same manner as in Example 1, a fluorine-containing alkoxysilane compound 6 was obtained. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 6 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 5 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Absorption by ester and ethoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 6 is shown in Table 1.
［実施例７］
反応容器中に、ジメチルスルホキシド、９−デセン−１−オール１．００部、及び過剰量の水素化ナトリウムを投入し、撹拌しながら室温で１時間反応させた。反応液をろ過後、反応容器中に、ろ液と１−ブロモパーフルオロヘキサン２．５５部を投入し、撹拌しながら室温で４８時間反応させた。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．４２部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物７を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物７をＮＭＲで測定し、−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエーテル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物７の構造を表１に示す。
[Example 7]
Into the reaction vessel, dimethyl sulfoxide, 1.00 parts of 9-decen-1-ol, and an excess amount of sodium hydride were added and reacted at room temperature for 1 hour with stirring. After filtering the reaction solution, the filtrate and 2.55 parts of 1-bromoperfluorohexane were put into a reaction vessel, and reacted at room temperature for 48 hours while stirring. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.42 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain a fluorine-containing alkoxysilane compound 7. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 7 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 10 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Further, absorption by ether and ethoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 7 is shown in Table 1.
［実施例８］
１０−ブロモ−１−デセンを原料として使用し、非特許文献（Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ，Ｃｏｌｌ．Ｖｏｌ．４，ｐ．４０１（１９６３）；Ｖｏｌ．３０，ｐ．３５（１９５０））の記載を参考にして９−デセン−１−チオールを合成した。反応容器中に、ジメチルスルホキシド、９−デセン−１−チオール１．００部、及び過剰量の水素化ナトリウムを投入し、撹拌しながら室温で１時間反応させた。反応液をろ過後、反応容器中に、ろ液と１−ブロモパーフルオロヘキサン２．３１部を投入し、撹拌しながら７０℃で５時間反応させた。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．４０部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物８を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物８をＮＭＲで測定し、−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてチオエーテル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物８の構造を表１に示す。
[Example 8]
Using 10-bromo-1-decene as a raw material, referring to the description of non-patent literature (Organic Synthesis, Coll. Vol. 4, p. 401 (1963); Vol. 30, p. 35 (1950)). 9-decene-1-thiol was synthesized. Into the reaction vessel, dimethyl sulfoxide, 1.00 part of 9-decene-1-thiol, and an excess amount of sodium hydride were added and reacted at room temperature for 1 hour with stirring. After filtering the reaction solution, the filtrate and 2.31 parts of 1-bromoperfluorohexane were put into a reaction vessel and reacted at 70 ° C. for 5 hours with stirring. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.40 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain fluorine-containing alkoxysilane compound 8. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 8 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 10 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Further, absorption by thioether and ethoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 8 is shown in Table 1.
［実施例９］
反応容器中に、９−デセン−１−チオール１．００部、パーフルオロヘプタン酸クロリド２．２２部、及びピリジンを投入し、撹拌しながら室温で反応させた。薄層クロマトグラフィーにより原料の消失を確認して反応終了とした。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．３８部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物９を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物９をＮＭＲで測定し、−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてチオエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物９の構造を表１に示す。
[Example 9]
Into the reaction vessel, 1.00 parts of 9-decene-1-thiol, 2.22 parts of perfluoroheptanoic acid chloride and pyridine were added and reacted at room temperature with stirring. The disappearance of the raw material was confirmed by thin layer chromatography, and the reaction was completed. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.38 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain a fluorine-containing alkoxysilane compound 9. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 9 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 10 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Further, absorption by thioester and ethoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 9 is shown in Table 1.
［比較例１］
反応容器中に、３−イソシアネートプロピルトリエトキシシラン１．００部及び少量の炭酸カリウムを投入して冷却下で撹拌した。その後、２−（パーフルオロヘキシル）エタノール１．４０部を滴下投入した。２−（パーフルオロヘキシル）エタノール投入後に、撹拌しながら室温で７時間反応させた。ろ過して炭酸カリウムを除去し、含フッ素アルコキシシラン化合物１０を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１０をＮＭＲで測定し、−（ＣＨ2）2−ＯＣＯＮＨ−（ＣＨ2）3−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてウレタン、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１０の構造を表１に示す。
[Comparative Example 1]
Into the reaction vessel, 1.00 part of 3-isocyanatopropyltriethoxysilane and a small amount of potassium carbonate were added and stirred under cooling. Thereafter, 1.40 parts of 2- (perfluorohexyl) ethanol was added dropwise. After charging 2- (perfluorohexyl) ethanol, the mixture was reacted at room temperature for 7 hours with stirring. The potassium carbonate was removed by filtration to obtain a fluorine-containing alkoxysilane compound 10. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 10 was measured by NMR, and the proton of — (CH 2 ) 2 —OCONH— (CH 2 ) 3 —Si— (OCH 2 CH 3 ) 3 was measured. The signal and the fluorine integration ratio were confirmed. Moreover, the absorption by urethane and ethoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 10 is shown in Table 1.
［比較例２］
反応容器中に、２Ｈ，２Ｈ，３Ｈ，３Ｈ−パーフルオロノナン酸１．００部、ジフェニルホスホリルアジド０．７４部、及び３−ブテン−１−オール０．１９部を投入し、撹拌しながら加熱下で５時間反応させた。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．４３部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物１１を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１１をＮＭＲで測定し、−（ＣＨ2）2−ＮＨＣＯＯ−（ＣＨ2）4−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてウレタン、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１１の構造を表１に示す。
[Comparative Example 2]
In a reaction vessel, 1.00 part of 2H, 2H, 3H, 3H-perfluorononanoic acid, 0.74 part of diphenylphosphoryl azide, and 0.19 part of 3-buten-1-ol are added and heated with stirring. The reaction was allowed to proceed for 5 hours. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.43 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain a fluorinated alkoxysilane compound 11. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 11 was measured by NMR, and the proton of — (CH 2 ) 2 —NHCOO— (CH 2 ) 4 —Si— (OCH 2 CH 3 ) 3 was measured. The signal and the fluorine integration ratio were confirmed. Moreover, the absorption by urethane and ethoxysilyl was observed by FT-IR. Table 1 shows the structure of the resulting fluorine-containing alkoxysilane compound 11.
［比較例３］
９−デセン−１−オールを２−（パーフルオロヘキシル）エタノール１．００部に変更するとともに、トリデカフルオロヘプタン酸を４−ペンテン酸０．３３部に変更し、かつ、トリエトキシシランを０．４４部用いたこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物１２を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１２をＮＭＲで測定し、−（ＣＨ2）2−ＯＣＯ−（ＣＨ2）4−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１２の構造を表１に示す。
[Comparative Example 3]
9-decen-1-ol is changed to 1.00 parts of 2- (perfluorohexyl) ethanol, tridecafluoroheptanoic acid is changed to 0.33 parts of 4-pentenoic acid, and triethoxysilane is changed to 0 A fluorine-containing alkoxysilane compound 12 was obtained in the same manner as in Example 1 except that .44 parts was used. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 12 was measured by NMR, and protons due to — (CH 2 ) 2 —OCO— (CH 2 ) 4 —Si— (OCH 2 CH 3 ) 3 were measured. The signal and the fluorine integration ratio were confirmed. Absorption by ester and ethoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 12 is shown in Table 1.
［比較例４］
９−デセン−１−オールを３−ブテン−１−オール１．００部に変更するとともに、トリデカフルオロヘプタン酸を２Ｈ，２Ｈ，３Ｈ，３Ｈ−パーフルオロノナン酸６．５３部に変更し、かつ、トリエトキシシランを０．４４部用いたこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物１３を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１３をＮＭＲで測定し、−（ＣＨ2）2−ＣＯＯ−（ＣＨ2）4−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１３の構造を表１に示す。
[Comparative Example 4]
9-decen-1-ol was changed to 1.00 parts of 3-buten-1-ol and tridecafluoroheptanoic acid was changed to 6.53 parts of 2H, 2H, 3H, 3H-perfluorononanoic acid, In addition, a fluorine-containing alkoxysilane compound 13 was obtained in the same manner as in Example 1 except that 0.44 part of triethoxysilane was used. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 13 was measured by NMR, and protons due to — (CH 2 ) 2 —COO— (CH 2 ) 4 —Si— (OCH 2 CH 3 ) 3 were measured. The signal and the fluorine integration ratio were confirmed. Absorption by ester and ethoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 13 is shown in Table 1.
［比較例５］
９−デセン−１−オールを３−ブテン−１−オール１．００部に変更するとともに、１−ブロモパーフルオロヘキサンを１−ブロモ−１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクタン５．９２部に変更し、かつ、トリエトキシシランを０．４７部用いたこと以外は、前述の実施例７と同様にして含フッ素アルコキシシラン化合物１４を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１４をＮＭＲで測定し、−（ＣＨ2）2−Ｏ−（ＣＨ2）4−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエーテル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１４の構造を表１に示す。
[Comparative Example 5]
9-decen-1-ol was changed to 1.00 parts of 3-buten-1-ol and 1-bromoperfluorohexane was changed to 5.92 parts of 1-bromo-1H, 1H, 2H, 2H-perfluorooctane. The fluorine-containing alkoxysilane compound 14 was obtained in the same manner as in Example 7 except that 0.47 part of triethoxysilane was used. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 14 was measured by NMR, and protons due to — (CH 2 ) 2 —O— (CH 2 ) 4 —Si— (OCH 2 CH 3 ) 3 were measured. The signal and the fluorine integration ratio were confirmed. Further, absorption by ether and ethoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 14 is shown in Table 1.
［比較例６］
反応容器中に、４−ペンテン酸１．００部及び塩化チオニル３．５６部を投入し、撹拌しながら９０℃で３時間反応させた。反応液を減圧蒸留して４−ペンテン酸クロライドを得た。得られた４−ペンテン酸クロライド１．００部と１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクチルアミン２．７０部を反応容器中で撹拌しながら１００℃で５時間反応させた。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．４３部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物１５を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１５をＮＭＲで測定し、−（ＣＨ2）2−ＮＨＣＯ−（ＣＨ2）4−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてアミド、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１５の構造を表１に示す。
[Comparative Example 6]
In a reaction vessel, 1.00 part of 4-pentenoic acid and 3.56 part of thionyl chloride were added and reacted at 90 ° C. for 3 hours with stirring. The reaction solution was distilled under reduced pressure to obtain 4-pentenoic acid chloride. The resulting 4-pentenoic acid chloride (1.00 part) and 1H, 1H, 2H, 2H-perfluorooctylamine (2.70 part) were reacted at 100 ° C. for 5 hours with stirring in a reaction vessel. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.43 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain a fluorinated alkoxysilane compound 15. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 15 was measured by NMR, and protons of — (CH 2 ) 2 —NHCO— (CH 2 ) 4 —Si— (OCH 2 CH 3 ) 3 were measured. The signal and the fluorine integration ratio were confirmed. Absorption by amide and ethoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 15 is shown in Table 1.
［比較例７］
４−ペンテン酸を２Ｈ，２Ｈ，３Ｈ，３Ｈ−パーフルオロノナン酸１．００部に変更するとともに、塩化チオニルを０．９１部用いたこと以外は、前述の比較例６と同様にして２Ｈ，２Ｈ，３Ｈ，３Ｈ−パーフルオロノナン酸クロライドを得た。得られた２Ｈ，２Ｈ，３Ｈ，３Ｈ−パーフルオロノナン酸クロライド１．００部と３−ブテン−１−アミン０．１７部を反応容器中で撹拌しながら反応させた。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．４３部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物１６を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１６をＮＭＲで測定し、−（ＣＨ2）2−ＣＯＮＨ−（ＣＨ2）4−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてアミド、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１６の構造を表１に示す。
[Comparative Example 7]
The 4-pentenoic acid was changed to 1.00 part of 2H, 2H, 3H, 3H-perfluorononanoic acid and 0.91 part of thionyl chloride was used. 2H, 3H, 3H-perfluorononanoic acid chloride was obtained. The obtained 2H, 2H, 3H, 3H-perfluorononanoic acid chloride (1.00 part) and 3-buten-1-amine (0.17 part) were reacted in a reaction vessel while stirring. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.43 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain a fluorinated alkoxysilane compound 16. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 16 was measured by NMR, and protons of — (CH 2 ) 2 —CONH— (CH 2 ) 4 —Si— (OCH 2 CH 3 ) 3 were measured. The signal and the fluorine integration ratio were confirmed. Absorption by amide and ethoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 16 is shown in Table 1.
［比較例８］
反応容器中に、パーフルオロヘプタン酸クロリド１．００部及び３−ブテン−１−アミン０．１９部を投入し、撹拌しながら１００℃で５時間反応させた。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．４７部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物１７を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１７をＮＭＲで測定し、−ＣＯＮＨ−（ＣＨ2）4−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてアミド、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１７の構造を表１に示す。
[Comparative Example 8]
In a reaction vessel, 1.00 part of perfluoroheptanoic acid chloride and 0.19 part of 3-buten-1-amine were added and reacted at 100 ° C. for 5 hours with stirring. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.47 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain a fluorine-containing alkoxysilane compound 17. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 17 was measured by NMR, and the proton signal and fluorine integration ratio by —CONH— (CH 2 ) 4 —Si— (OCH 2 CH 3 ) 3 were determined. confirmed. Absorption by amide and ethoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 17 is shown in Table 1.
［比較例９］
９−デセン−１−オールをアリルアルコール１．００部に変更するとともに、トリデカフルオロヘプタン酸をパーフルオロオクタン酸８．５６部に変更し、かつ、トリエトキシシランをトリメトキシシラン０．３２部に変更したこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物１８を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１８をＮＭＲで測定し、−（ＣＨ2）3−Ｓｉ−（ＯＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、メトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１８の構造を表１に示す。
[Comparative Example 9]
9-decen-1-ol is changed to 1.00 parts of allyl alcohol, tridecafluoroheptanoic acid is changed to 8.56 parts of perfluorooctanoic acid, and triethoxysilane is changed to 0.32 parts of trimethoxysilane. A fluorine-containing alkoxysilane compound 18 was obtained in the same manner as in Example 1 except that the above was changed. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 18 was measured by NMR, and the proton signal and fluorine integration ratio due to — (CH 2 ) 3 —Si— (OCH 3 ) 3 were confirmed. Absorption by ester and methoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 18 is shown in Table 1.
［比較例１０］
９−デセン−１−オールを３−ブテン−１−オール１．００部に変更するとともに、トリエトキシシランをトリメトキシシラン０．３８部に変更し、かつ、１−ブロモパーフルオロヘキサンを５．５３部用いたこと以外は、前述の実施例７と同様にして含フッ素アルコキシシラン化合物１９を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物１９をＮＭＲで測定し、−（ＣＨ2）4−Ｓｉ−（ＯＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエーテル、メトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物１９の構造を表１に示す。
[Comparative Example 10]
9-decene-1-ol is changed to 1.00 part of 3-buten-1-ol, triethoxysilane is changed to 0.38 part of trimethoxysilane, and 1-bromoperfluorohexane is changed to 5. A fluorine-containing alkoxysilane compound 19 was obtained in the same manner as in Example 7 except that 53 parts were used. In the same manner as in Example 1, the fluorine-containing alkoxysilane compound 19 obtained were measured with NMR, - (CH 2) 4 -Si- (OCH 3) 3 by confirming the signal and fluorine integration ratio of protons. Further, absorption by ether and methoxysilyl was observed by FT-IR. The structure of the resulting fluorine-containing alkoxysilane compound 19 is shown in Table 1.
［比較例１１］
２１−ドコセン酸を原料として使用し、非特許文献（Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ，Ｃｏｌｌ．Ｖｏｌ．１，ｐ．３０６（１９４１）；Ｖｏｌ．６，ｐ．５４（１９２６））の記載を参考にして２１−ドコセン−１−オールを合成した。そして、９−デセン−１−オールを２１−ドコセン−１−オール１．００部に変更するとともに、トリデカフルオロヘプタン酸を１．３５部及びトリエトキシシランを０．２９部用いたこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物２０を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物２０をＮＭＲで測定し、−（ＣＨ2）22−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物２０の構造を表１に示す。
[Comparative Example 11]
Using 21-docosenoic acid as a raw material, 21-docosene was described with reference to the description of non-patent literature (Organic Synthesis, Coll. Vol. 1, p. 306 (1941); Vol. 6, p. 54 (1926)). -1-ol was synthesized. And 9-decene-1-ol was changed to 1.00 parts of 21-docosen-1-ol, except that 1.35 parts of tridecafluoroheptanoic acid and 0.29 parts of triethoxysilane were used. In the same manner as in Example 1, the fluorine-containing alkoxysilane compound 20 was obtained. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 20 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 22 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Absorption by ester and ethoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 20 is shown in Table 1.
［比較例１２］
トリデカフルオロヘプタンをトリフルオロ酢酸０．８８部に変更するとともに、トリエトキシシランを０．７８部用いたこと以外は、前述の実施例１と同様にして含フッ素アルコキシシラン化合物２１を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物２１をＮＭＲで測定し、−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナル及びフッ素積分比を確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られた含フッ素アルコキシシラン化合物２１の構造を表１に示す。
[Comparative Example 12]
A fluorine-containing alkoxysilane compound 21 was obtained in the same manner as in Example 1 except that tridecafluoroheptane was changed to 0.88 part of trifluoroacetic acid and 0.78 part of triethoxysilane was used. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 21 was measured by NMR, and the proton signal and fluorine integration ratio by — (CH 2 ) 10 —Si— (OCH 2 CH 3 ) 3 were confirmed. . Absorption by ester and ethoxysilyl was observed by FT-IR. The structure of the obtained fluorine-containing alkoxysilane compound 21 is shown in Table 1.
［比較例１３］
ヘプタン酸１．００部と塩化チオニル２．７４部を使用し、前述の比較例６と同様にしてヘプタン酸クロライドを得た。得られたヘプタン酸クロライド１．００部と９−デセン−１−オール０．９５部を反応容器中で撹拌しながら１００℃で５時間反応させた。反応液をフッ素系溶媒と水で分液した後、フッ素系溶媒層を回収して濃縮し、中間体を得た。得られた中間体１．００部とトリエトキシシラン０．６９部を反応容器中で撹拌しながら８０℃で２時間反応させ、含フッ素アルコキシシラン化合物２２を得た。実施例１と同様にして、得られた含フッ素アルコキシシラン化合物２２をＮＭＲで測定し、Ｃ6Ｈ13−ＣＯＯ−（ＣＨ2）10−Ｓｉ−（ＯＣＨ2ＣＨ3）3によるプロトンのシグナルを確認した。また、ＦＴ−ＩＲにてエステル、エトキシシリルによる吸収を観測した。得られたアルコキシシラン化合物２２の構造を表１に示す。
[Comparative Example 13]
Heptanoic acid chloride was obtained in the same manner as in Comparative Example 6 using 1.00 part of heptanoic acid and 2.74 parts of thionyl chloride. The resulting heptanoic acid chloride (1.00 part) and 9-decen-1-ol (0.95 part) were reacted at 100 ° C. for 5 hours with stirring in a reaction vessel. The reaction solution was separated with a fluorinated solvent and water, and then the fluorinated solvent layer was collected and concentrated to obtain an intermediate. 1.00 part of the obtained intermediate and 0.69 part of triethoxysilane were reacted at 80 ° C. for 2 hours with stirring in a reaction vessel to obtain a fluorine-containing alkoxysilane compound 22. In the same manner as in Example 1, the obtained fluorine-containing alkoxysilane compound 22 was measured by NMR, and the proton signal due to C 6 H 13 —COO— (CH 2 ) 10 —Si— (OCH 2 CH 3 ) 3 was measured. confirmed. Absorption by ester and ethoxysilyl was observed by FT-IR. The structure of the resulting alkoxysilane compound 22 is shown in Table 1.
（２）撥水膜の作製
［実施例１０］
商品名「Ｎｏｖｅｃ（登録商標）７２００」（３Ｍ社製）：エタノール＝１：１溶液を使用し、含フッ素アルコキシシラン化合物１を固形分０．５％となるように希釈した。スピンコーターを使用して得られた希釈液をスライドガラス上に塗布した後、８０℃で２時間乾燥させて撥水膜１を作製した。
(2) Production of water-repellent film [Example 10]
Product name “Novec (registered trademark) 7200” (manufactured by 3M): Ethanol = 1: 1 solution was used, and the fluorine-containing alkoxysilane compound 1 was diluted to a solid content of 0.5%. The diluted solution obtained using a spin coater was applied on a slide glass, and then dried at 80 ° C. for 2 hours to produce a water-repellent film 1.
［実施例１１〜１８、比較例１４〜２６］
含フッ素アルコキシシラン化合物１を含フッ素アルコキシシラン化合物２〜２１、及びアルコキシシラン化合物２２に変更したこと以外は、前述の実施例１０と同様にして撥水膜２〜２２を作製した。
[Examples 11 to 18, Comparative Examples 14 to 26]
Water-repellent films 2 to 22 were produced in the same manner as in Example 10 except that the fluorine-containing alkoxysilane compound 1 was changed to the fluorine-containing alkoxysilane compounds 2 to 21 and the alkoxysilane compound 22.
（３）評価
［撥水性の評価］
自動接触角計（ＣＡ−ＶＰ、協和界面化学社製）を使用し、作製した撥水膜表面の接触角を測定した。具体的には、作製した撥水膜表面上の異なる５箇所で水の静的接触角を測定した。次いで、測定した静的接触角の最大値と最小値を切り捨てた３点の平均値を算出し、以下に示す評価基準に従って撥水膜の撥水性を評価した。結果を表２に示す。
◎：静的接触角の平均値が１００°以上
○：９０°以上１００°未満
△：８０°以上９０°未満
×：８０°未満
(3) Evaluation [Evaluation of water repellency]
Using an automatic contact angle meter (CA-VP, manufactured by Kyowa Interface Chemical Co., Ltd.), the contact angle of the produced water-repellent film surface was measured. Specifically, the static contact angles of water were measured at five different locations on the produced water-repellent film surface. Next, an average value of three points obtained by discarding the maximum value and the minimum value of the measured static contact angle was calculated, and the water repellency of the water-repellent film was evaluated according to the following evaluation criteria. The results are shown in Table 2.
A: The average value of static contact angles is 100 ° or more. ○: 90 ° or more and less than 100 °. Δ: 80 ° or more and less than 90 °.
［耐久性］
撥水膜を形成したスライドガラスを６０℃の１．０×１０-4規定の水酸化ナトリウム水溶液中に浸漬した。１週間後にスライドガラスを取り出し、表面をアセトンで洗い流して乾燥させた。次いで、前述の［撥水性の評価］の場合と同様にして撥水膜表面の静的接触角を測定し、３点の平均値を算出した。そして、浸漬前の撥水膜の撥水膜表面の静的接触角と、浸漬前の撥水膜の撥水膜表面の静的接触角を比較し、以下に示す評価基準に従って撥水膜の耐久性を評価した。評価結果を表２に示す。
◎：浸漬後の静的接触角が、浸漬前の静的接触角の９０％以上
○：浸漬後の静的接触角が、浸漬前の静的接触角の７５％以上９０％未満
△：浸漬後の静的接触角が、浸漬前の静的接触角の６０％以上７５％未満
×：浸漬後の静的接触角が、浸漬前の静的接触角の６０％未満
[durability]
The slide glass on which the water-repellent film was formed was immersed in a 1.0 × 10 −4 normal sodium hydroxide aqueous solution at 60 ° C. One week later, the slide glass was taken out, and the surface was washed with acetone and dried. Subsequently, the static contact angle on the surface of the water-repellent film was measured in the same manner as in the case of [Evaluation of water repellency] described above, and an average value of three points was calculated. Then, the static contact angle of the water-repellent film surface of the water-repellent film before immersion and the static contact angle of the water-repellent film surface of the water-repellent film before immersion are compared, and Durability was evaluated. The evaluation results are shown in Table 2.
◎: Static contact angle after immersion is 90% or more of static contact angle before immersion ○: Static contact angle after immersion is 75% or more and less than 90% of static contact angle before immersion Δ: Immersion The static contact angle after immersion is 60% or more and less than 75% of the static contact angle before immersion. X: The static contact angle after immersion is less than 60% of the static contact angle before immersion.
表２に示す評価結果から明らかなように、実施例１〜９の含フッ素アルコキシシラン化合物を用いて作製した撥水膜は、比較例１〜１２の含フッ素アルコキシシラン化合物、及び比較例１３のアルコキシシラン化合物を用いて作製した撥水膜に比して、十分に優れた撥水性及び耐久性を発揮するものであった。 As is clear from the evaluation results shown in Table 2, the water-repellent films produced using the fluorine-containing alkoxysilane compounds of Examples 1 to 9 were the fluorine-containing alkoxysilane compounds of Comparative Examples 1 to 12 and Comparative Example 13 Compared to a water-repellent film produced using an alkoxysilane compound, it exhibited sufficiently excellent water repellency and durability.
本発明の含フッ素アルコキシシラン化合物をコーティング剤として使用すれば、環境問題に配慮しつつ、撥水性及び耐久性に優れた撥水膜を形成することができる。 If the fluorine-containing alkoxysilane compound of the present invention is used as a coating agent, a water-repellent film excellent in water repellency and durability can be formed while considering environmental problems.
Claims (4)
Ｒｆ−Ａ−Ｂ−ＳｉＸ3 ・・・（１）
（前記一般式（１）中、Ｒｆは炭素数３〜６のパーフルオロアルキル基を示し、Ａは−ＣＯＯ−、−Ｏ−、−Ｓ−、又は−ＣＯ−Ｓ−を示し、Ｂは−（ＣＨ2）m−（ｍ＝５〜２０）を示し、Ｘは−ＯＣnＨ2n+1（ｎ＝１〜４）を示し、３つのＸは互いに同一でも異なっていてもよい） A fluorine-containing alkoxysilane compound represented by the following general formula (1).
Rf-A-B-SiX 3 (1)
(In the general formula (1), Rf represents a perfluoroalkyl group of 3-6 carbon atoms, A is -COO -, - O -, - S-, or -CO-S- are shown, the B - (CH 2 ) m — (m = 5 to 20), X represents —OC n H 2n + 1 (n = 1 to 4), and three Xs may be the same or different from each other)
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