JP6691296B2 - Water-repellent liquid, water-repellent article and manufacturing method thereof - Google Patents
Water-repellent liquid, water-repellent article and manufacturing method thereof Download PDFInfo
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- JP6691296B2 JP6691296B2 JP2016138539A JP2016138539A JP6691296B2 JP 6691296 B2 JP6691296 B2 JP 6691296B2 JP 2016138539 A JP2016138539 A JP 2016138539A JP 2016138539 A JP2016138539 A JP 2016138539A JP 6691296 B2 JP6691296 B2 JP 6691296B2
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- water
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- repellent
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- 239000005871 repellent Substances 0.000 title claims description 164
- 239000007788 liquid Substances 0.000 title claims description 92
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 117
- -1 siloxane compound Chemical class 0.000 claims description 77
- 150000001875 compounds Chemical class 0.000 claims description 69
- 238000000576 coating method Methods 0.000 claims description 63
- 230000002940 repellent Effects 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 35
- 125000003545 alkoxy group Chemical group 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 27
- 239000011521 glass Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 8
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 239000002585 base Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 14
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 14
- 238000005299 abrasion Methods 0.000 description 10
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 8
- 229940126062 Compound A Drugs 0.000 description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 239000005357 flat glass Substances 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 125000005372 silanol group Chemical group 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 239000012024 dehydrating agents Substances 0.000 description 3
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- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WBGKAOURNYRYBT-UHFFFAOYSA-N 2-sulfopropanoic acid Chemical compound OC(=O)C(C)S(O)(=O)=O WBGKAOURNYRYBT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- NSRGOAGKXKNHQX-UHFFFAOYSA-N 2-hydroxybutane-1-sulfonic acid Chemical compound CCC(O)CS(O)(=O)=O NSRGOAGKXKNHQX-UHFFFAOYSA-N 0.000 description 1
- RIYJUQDMHMUBMK-UHFFFAOYSA-N 2-hydroxypentane-1-sulfonic acid Chemical compound CCCC(O)CS(O)(=O)=O RIYJUQDMHMUBMK-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- OURSFPZPOXNNKX-UHFFFAOYSA-N 3-sulfopropanoic acid Chemical compound OC(=O)CCS(O)(=O)=O OURSFPZPOXNNKX-UHFFFAOYSA-N 0.000 description 1
- JXBUOZMYKQDZFY-UHFFFAOYSA-N 4-hydroxybenzene-1,3-disulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1S(O)(=O)=O JXBUOZMYKQDZFY-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000005338 frosted glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
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- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007372 rollout process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
Description
本発明は、各種基材に撥水性被膜を形成するために用いる撥水液、該撥水液を用いて得られる撥水性物品及びその製造方法に関する。 The present invention relates to a water repellent liquid used for forming a water repellent coating film on various substrates, a water repellent article obtained by using the water repellent liquid, and a method for producing the same.
撥水性を有する撥水ガラスは、雨天時、雨滴をはじくため、室内から室外への良好な視界が保たれる。このため、撥水ガラスは、建築、車両、船舶、航空機など種々の分野にて、使用されている。特に、水滴が滑りやすい滑水性の優れた撥水ガラスは、雨滴除去性が良好なため、雨天運転時の安全性が格段に向上する。このため、実使用に耐えうる耐久性を有する滑水性の優れた撥水ガラスが望まれている。また、滑水性の優れた撥水性材料は、着氷、着雪を低減させる効果も有しているため、豪雪地域の電線や屋外アンテナ向けの撥水性物品としても期待されている。 The water-repellent glass, which has water repellency, repels raindrops in the case of rain, so that a good visibility from the inside to the outside can be maintained. For this reason, water-repellent glass is used in various fields such as construction, vehicles, ships, and aircraft. In particular, the water-repellent glass, which has excellent water-sliding property in which water droplets are slippery, has a good raindrop removal property, so that the safety during rainy operation is significantly improved. Therefore, a water-repellent glass having excellent durability and durability that can withstand actual use is desired. Further, since the water-repellent material having excellent water-slipping property also has an effect of reducing ice accretion and snow accretion, it is expected as a water-repellent article for electric wires and outdoor antennas in heavy snowfall areas.
近年、フルオロアルキルシラン系化合物において、フルオロカーボンユニットの数（ＣＦ３とＣＦ２の総数）が大きなもの、例えば、フルオロカーボンユニットの数が８以上のフルオロアルキルシラン系化合物（以降、「長鎖のフルオロアルキルシラン系化合物」と記載する場合がある）については、その合成プロセスで副生成物として排出されるＰＦＯＡ(perfluorooctanoic acid)に対する環境への負荷の懸念が明らかとなったため、２００３年４月にＥＰＡ（米国環境保護庁）がＰＦＯＡに対する科学的調査を強化する旨を発表以来、長鎖のフルオロアルキルシラン系化合物は入手困難な状況となった。 In recent years, among fluoroalkylsilane compounds, those having a large number of fluorocarbon units (the total number of CF 3 and CF 2 ), for example, fluoroalkylsilane compounds having 8 or more fluorocarbon units (hereinafter referred to as “long-chain fluoroalkyl units”). (Silane compound) may be referred to as "silane compound"), and it became clear that environmental impact on PFOA (perfluorooctanoic acid) emitted as a by-product in the synthesis process was confirmed in April 2003. Long-chain fluoroalkylsilane compounds have become difficult to obtain since the United States Environmental Protection Agency) announced that it would strengthen scientific research on PFOA.
一方、フルオロアルキルシラン系化合物におけるフルオロカーボンユニット数と、撥水性及び滑水性には関係性があり、フルオロカーボンユニット数が少なくなるにつれ、化合物の剛直性が低くなり、基材表面に綺麗に配列し難くなる傾向にある。特にフルオロカーボンユニットの数が７以下の場合は、その傾向が強くなり、結果、撥水性及び滑水性が低下してしまう傾向がある。 On the other hand, there is a relationship between the number of fluorocarbon units in the fluoroalkylsilane compound and the water repellency and water sliding property. As the number of fluorocarbon units decreases, the rigidity of the compound decreases and it becomes difficult to arrange them neatly on the substrate surface. Tends to become. In particular, when the number of fluorocarbon units is 7 or less, the tendency becomes strong, and as a result, the water repellency and the water slide tend to decrease.
そのため、フルオロカーボンユニットの数が７以下のフルオロアルキルシラン系化合物を用いても、長鎖のフルオロアルキルシラン系化合物と同様の撥水性及び滑水性を備えつつ、耐久性を有する撥水膜及び該撥水膜を形成出来る処理剤が強く求められている。 Therefore, even if a fluoroalkylsilane-based compound having 7 or less fluorocarbon units is used, the water-repellent film and the water-repellent film having the same water repellency and sliding property as those of the long-chain fluoroalkylsilane-based compound and having durability There is a strong demand for a treatment agent capable of forming a water film.
特許文献１には、フルオロカーボンユニットの数が４のフルオロアルキルシラン系化合物と、ポリジメチルシロキサンの側鎖が変性され、メトキシ基を３つ有する化合物との共加水分解物について記載されている。 Patent Document 1 describes a cohydrolyzate of a fluoroalkylsilane compound having four fluorocarbon units and a compound in which the side chain of polydimethylsiloxane is modified and which has three methoxy groups.
しかし、フルオロカーボンユニットの数が７以下のフルオロアルキルシラン系化合物と、ポリジメチルシロキサンの側鎖が変性され、アルコキシ基を３つ有する化合物とを含む撥水液を用いて撥水性被膜を形成した場合、撥水性は良好なものの、滑水性が不十分なことがあり、滑水性を向上する余地があった（後述の比較例８等参照）。 However, when a water-repellent film is formed using a water-repellent liquid containing a fluoroalkylsilane compound having 7 or less fluorocarbon units and a compound in which the side chains of polydimethylsiloxane are modified and which has three alkoxy groups. Although the water repellency was good, the water sliding property was sometimes insufficient, and there was room for improving the water sliding property (see Comparative Example 8 and the like described later).
そこで、本発明は、良好な滑水性を有する撥水性被膜を形成することが出来る、フルオロカーボンユニットの数が７以下のフルオロアルキルシラン系化合物を含む撥水液、該撥水液を用いて得られる撥水性物品及びその製造方法を提供することを課題とする。 Therefore, the present invention provides a water-repellent liquid containing a fluoroalkylsilane compound having a fluorocarbon unit number of 7 or less, which can form a water-repellent coating having good water-sliding property, and is obtained by using the water-repellent liquid. An object is to provide a water repellent article and a method for manufacturing the same.
本発明者らは、上記課題に鑑み、鋭意検討した結果、特定のシロキサン化合物（側鎖が変性されたポリジメチルシロキサン）を、フルオロカーボンユニットの数が７以下の特定のフルオロアルキルシラン系化合物、有機溶媒、水、酸触媒とともに撥水液に含有させ、各原料を特定の混合比率とすることで、良好な滑水性能を有する撥水性被膜を形成することが出来ることを見出し、本発明に到達した。 In view of the above problems, the inventors of the present invention have made extensive studies and found that a specific siloxane compound (polydimethylsiloxane having a modified side chain) is a specific fluoroalkylsilane compound having 7 or less fluorocarbon units, an organic compound. It was found that a water-repellent coating having good water-sliding performance can be formed by containing a solvent, water, and an acid catalyst in a water-repellent liquid and making each raw material have a specific mixing ratio, and arrived at the present invention. did.
すなわち、本発明の撥水液は、以下の発明を含む。
［発明１］
一般式［１］で表されるフルオロアルキルシラン系化合物、
一般式［２−１］又は一般式［２−２］で表されるシロキサン化合物の少なくとも１つ、
有機溶媒、水、及び、酸
を含み、該フルオロアルキルシラン系化合物と該シロキサン化合物の質量比が１：１〜１：４である、撥水性被膜を形成するための撥水液。
［発明２］
前記一般式［２−１］で表されるシロキサン化合物において、Ｙが、アルコキシ基であることを特徴とする、発明１に記載の撥水液。
［発明３］
前記一般式［２−１］で表されるシロキサン化合物において、Ｙが、それぞれ独立してメトキシ基、エトキシ基及びプロポキシ基からなる群から選ばれる１つの基であることを特徴とする、発明１に記載の撥水液。
［発明４］
前記一般式［２−２］で表されるシロキサン化合物において、Ｚが、アルコキシ基であることを特徴とする、発明１に記載の撥水液。
［発明５］
前記一般式［２−２］で表されるシロキサン化合物において、Ｚが、それぞれ独立してメトキシ基、エトキシ基及びプロポキシ基からなる群から選ばれる１つの基であることを特徴とする、発明１に記載の撥水液。
［発明６］
前記一般式［１］で表されるフルオロアルキルシラン系化合物と、前記一般式［２−１］及び前記一般式［２−２］で表されるシロキサン化合物の質量比が、１：２〜１：３の質量比であることを特徴とする、発明１に記載の撥水液。
［発明７］
前記酸が、有機スルホン酸であることを特徴とする、発明１に記載の撥水液。
［発明８］
前記一般式［１］で表されるフルオロアルキルシラン系化合物において、ｍが２〜７の整数であり、ｎが１〜３の整数であり、Ｘがそれぞれ独立してアルコキシ基であり、ｐが３であることを特徴とする、発明１に記載の撥水液。
［発明９］
前記一般式［１］で表されるフルオロアルキルシラン系化合物において、ｍが４〜６の整数であり、ｎが１〜３の整数であり、Ｘがそれぞれ独立してアルコキシ基であり、ｐが３であることを特徴とする、発明１に記載の撥水液。
［発明１０］
一般式［１−Ａ］で表されるフルオロアルキルシラン系化合物、
一般式［２−１−Ａ］で表されるシロキサン化合物、
有機溶媒、水、及び、酸
を含み、該フルオロアルキルシラン系化合物と該シロキサン化合物の質量比が１：２〜１：３である、撥水性被膜を形成するための撥水液。
［発明１１］
前記一般式［１］で表されるフルオロアルキルシラン系化合物と、前記一般式［２−１］又は［２−２］で表されるシロキサン化合物の少なくとも１つとの部分加水分解重縮合物を含むことを特徴とする、撥水性被膜。
［発明１２］
基材と、該基材上に撥水性被膜を有する撥水性物品の製造方法であって、該撥水性被膜が、発明１に記載の撥水液を該基材の表面上に塗布することにより形成されることを特徴とする、撥水性物品の製造方法。
［発明１３］
発明１に記載の撥水液を基材の表面上に塗布した後、５０〜３５０℃で１〜６０分間加熱することを特徴とする、発明１２に記載の撥水性物品の製造方法。
［発明１４］
発明１に記載の撥水液を基材の表面上に塗布する方法が、手塗り法であることを特徴とする、発明１２に記載の撥水性物品の製造方法。
［発明１５］
撥水性被膜の膜厚が、１０ｎｍ未満１ｎｍ以上であることを特徴とする、発明１２に記載の撥水性物品の製造方法。
［発明１６］
前記基材がガラス基材であることを特徴とする、発明１２に記載の撥水性物品の製造方法。
That is, the water repellent liquid of the present invention includes the following inventions.
[Invention 1]
A fluoroalkylsilane compound represented by the general formula [1],
At least one siloxane compound represented by the general formula [2-1] or the general formula [2-2],
A water-repellent liquid for forming a water-repellent coating film, which contains an organic solvent, water, and an acid, and has a mass ratio of the fluoroalkylsilane compound to the siloxane compound of 1: 1 to 1: 4.
[Invention 2]
The water repellent liquid according to invention 1, wherein Y is an alkoxy group in the siloxane compound represented by the general formula [2-1].
[Invention 3]
In the siloxane compound represented by the general formula [2-1], Y is each independently one group selected from the group consisting of a methoxy group, an ethoxy group, and a propoxy group. The water repellent liquid described in.
[Invention 4]
The water-repellent liquid according to invention 1, wherein Z is an alkoxy group in the siloxane compound represented by the general formula [2-2].
[Invention 5]
In the siloxane compound represented by the general formula [2-2], each Z is independently one group selected from the group consisting of a methoxy group, an ethoxy group, and a propoxy group. The water repellent liquid described in.
[Invention 6]
The mass ratio of the fluoroalkylsilane compound represented by the general formula [1] to the siloxane compound represented by the general formula [2-1] and the general formula [2-2] is 1: 2-1. The water repellent liquid according to invention 1, wherein the water repellent liquid has a mass ratio of 3: 1.
[Invention 7]
The water repellent liquid according to invention 1, wherein the acid is an organic sulfonic acid.
[Invention 8]
In the fluoroalkylsilane compound represented by the general formula [1], m is an integer of 2 to 7, n is an integer of 1 to 3, X is each independently an alkoxy group, and p is 3. The water-repellent liquid according to invention 1, which is 3.
[Invention 9]
In the fluoroalkylsilane-based compound represented by the general formula [1], m is an integer of 4 to 6, n is an integer of 1 to 3, X is each independently an alkoxy group, and p is p. 3. The water-repellent liquid according to invention 1, which is 3.
[Invention 10]
A fluoroalkylsilane compound represented by the general formula [1-A],
A siloxane compound represented by the general formula [2-1-A],
A water-repellent liquid for forming a water-repellent film, which contains an organic solvent, water, and an acid, and has a mass ratio of the fluoroalkylsilane compound to the siloxane compound of 1: 2 to 1: 3.
[Invention 11]
A partially hydrolyzed polycondensate of a fluoroalkylsilane compound represented by the general formula [1] and at least one siloxane compound represented by the general formula [2-1] or [2-2] is included. A water-repellent coating characterized by the following.
[Invention 12]
A method for producing a water-repellent article having a base material and a water-repellent coating film on the base material, wherein the water-repellent coating film is formed by applying the water-repellent liquid according to Invention 1 on the surface of the base material. A method for producing a water-repellent article, which is characterized by being formed.
[Invention 13]
The method for producing a water-repellent article according to the invention 12, wherein the water-repellent liquid according to the invention 1 is applied onto the surface of a substrate and then heated at 50 to 350 ° C. for 1 to 60 minutes.
[Invention 14]
The method for producing a water-repellent article according to the invention 12, wherein the method for applying the water-repellent liquid according to the invention 1 to the surface of the substrate is a hand coating method.
[Invention 15]
13. The method for producing a water-repellent article according to invention 12, wherein the film thickness of the water-repellent coating is less than 10 nm and 1 nm or more.
[Invention 16]
13. The method for producing a water-repellent article according to invention 12, wherein the base material is a glass base material.
本発明によると、フルオロカーボンユニットの数が７以下のフルオロアルキルシラン系化合物を含む撥水液を用いて、良好な滑水性を有する撥水性被膜を形成することが出来る。 According to the present invention, a water-repellent coating having good water-sliding property can be formed using a water-repellent liquid containing a fluoroalkylsilane compound having 7 or less fluorocarbon units.
以下、本発明の実施形態について具体的に説明する。しかしながら、本発明は、以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。 Hereinafter, embodiments of the present invention will be specifically described. However, the present invention is not limited to the following embodiments, and can be appropriately modified and applied within a range not changing the gist of the present invention.
＜フルオロアルキルシラン系化合物＞
本発明の撥水液においては、下記一般式［１］で表されるフルオロアルキルシラン系化合物が用いられる。
In the water repellent liquid of the present invention, a fluoroalkylsilane compound represented by the following general formula [1] is used.
フルオロカーボンユニットの数（ＣＦ３とＣＦ２の総数）ｍが増加すると、得られる撥水性被膜の耐候性、耐摩耗性は改善する。しかしながら、 前記背景の通り、ｍの数が大きなフルオロアルキルシラン系化合物は入手が困難になっている。一方、ｍの数が小さいフルオロアルキルシラン系化合物では、フルオロアルキルシラン鎖が短いため、撥水性被膜の撥水性・耐摩耗性が不十分であった（後述の比較例１７参照）。そこで、ｍは２〜７の整数とした。 When the number of fluorocarbon units (the total number of CF 3 and CF 2 ) m increases, the weather resistance and abrasion resistance of the obtained water-repellent coating are improved. However, as described above, it is difficult to obtain a fluoroalkylsilane compound having a large number of m. On the other hand, in the fluoroalkylsilane compound having a small number of m, the fluoroalkylsilane chain was short, and therefore the water repellent coating had insufficient water repellency and abrasion resistance (see Comparative Example 17 described later). Therefore, m is an integer of 2 to 7.
前記一般式［１］で表されるフルオロアルキルシラン系化合物としては、例えば、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣＨ3（ＯＣＨ3）2、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2ＯＣＨ3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2ＳｉＣＨ3（ＯＣＨ3）2、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2ＯＣＨ3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣｌ3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2ＳｉＣＨ3Ｃｌ2、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2Ｃｌ、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2ＳｉＣｌ3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2ＳｉＣＨ3Ｃｌ2、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＣＨ3）2Ｃｌ等が使用できる。入手容易性と、得られる撥水性物品における撥水性被膜の耐久性の観点から、前記一般式［１］のｍが４〜６の整数、及び／又は、ｎが１〜３の整数であるフルオロアルキルシラン系化合物が好ましい。 Examples of the fluoroalkylsilane compound represented by the general formula [1] include CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OCH 3 ) 3 and CF 3 (CF 2 ) 5 CH 2 CH 2 Si. (OC 2 H 5 ) 3 , CF 3 (CF 2 ) 5 CH 2 CH 2 SiCH 3 (OCH 3 ) 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 Si (CH 3 ) 2 OCH 3 , CF 3 ( CF 2) 3 CH 2 CH 2 Si (OCH 3) 3, CF 3 (CF 2) 3 CH 2 CH 2 SiCH 3 (OCH 3) 2, CF 3 (CF 2) 3 CH 2 CH 2 Si (CH 3) 2 OCH 3 , CF 3 (CF 2 ) 5 CH 2 CH 2 SiCl 3 , CF 3 (CF 2 ) 5 CH 2 CH 2 SiCH 3 Cl 2 , CF 3 (CF 2 ) 5 CH 2 CH 2 Si (CH 3 ) 2 Cl, CF 3 (CF 2 ) 3 CH 2 CH 2 SiCl 3, CF 3 (CF 2) 3 CH 2 CH 2 S CH 3 Cl 2, CF 3 ( CF 2) 3 CH 2 CH 2 Si (CH 3) 2 Cl and the like can be used. From the viewpoint of easy availability and durability of the water-repellent coating in the resulting water-repellent article, fluoro in which m in the general formula [1] is an integer of 4 to 6 and / or n is an integer of 1 to 3. Alkylsilane compounds are preferred.
また、前記一般式[１]において、Ｘとしては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等のアルコキシ基、クロロ基、イソシアネート基又はヒドロキシル基を用いることができる。ただし、これらの官能基の反応性が高すぎると、撥水液調合時の取扱いが難しくなるだけでなく、撥水液のポットライフが短くなる場合がある。一方、反応性が低すぎると、反応が十分進行しなくなり、生成するシラノール基の量が十分でなくなるため、基材と得られる撥水性被膜の結合が十分でなくなり、撥水性被膜の耐候性、耐摩耗性が低くなる場合がある。取扱いの容易さ、撥水液のポットライフ、得られる撥水性被膜の耐候性、耐摩耗性を考慮すると、Ｘとしてはアルコキシ基が好ましく、中でもメトキシ基、エトキシ基が特に好ましい。さらに、基材と反応可能な官能基Ｘの数は、１分子あたり１〜３個であるが、Ｘの数が多いほど、基材と得られる撥水性被膜の結合が十分になり耐久性がよくなるので３個が好ましい。 Further, in the above general formula [1], as X, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a chloro group, an isocyanate group or a hydroxyl group can be used. However, if the reactivity of these functional groups is too high, not only the handling during preparation of the water-repellent liquid becomes difficult, but also the pot life of the water-repellent liquid may be shortened. On the other hand, if the reactivity is too low, the reaction does not proceed sufficiently and the amount of silanol groups produced is not sufficient, so that the bond between the base material and the water-repellent coating obtained is insufficient, and the weather resistance of the water-repellent coating, Wear resistance may be reduced. Considering the ease of handling, the pot life of the water repellent liquid, and the weather resistance and abrasion resistance of the resulting water repellent coating, X is preferably an alkoxy group, and particularly preferably a methoxy group or an ethoxy group. Further, the number of functional groups X capable of reacting with the base material is 1 to 3 per molecule, but the larger the number of X is, the more sufficient the bond between the base material and the water-repellent coating obtained is, resulting in durability. 3 is preferable because it improves.
撥水液を塗布する基材がガラス基材の場合、前記一般式［１］で表されるフルオロアルキルシラン系化合物は、片側末端に、ガラス基材表面のシラノール基と反応可能な官能基Ｘを有している。このような官能基を両側末端に有するフルオロアルキルシラン系化合物を撥水液が含む場合、撥水液をガラス基材に塗布・乾燥後、該フルオロアルキルシラン系化合物が余剰分となり易く、この余剰分はガラス基材に強固に固着し、乾燥後の余剰分の除去が困難となる傾向がある。そのため、片側末端のみにシラノール基と反応可能な官能基を有するフルオロアルキルシラン系化合物が好適に用いられる。 When the substrate to which the water-repellent liquid is applied is a glass substrate, the fluoroalkylsilane compound represented by the general formula [1] has a functional group X at one end that can react with the silanol group on the surface of the glass substrate. have. When the water repellent liquid contains a fluoroalkylsilane compound having such functional groups at both ends, after the water repellent liquid is applied to the glass substrate and dried, the fluoroalkylsilane compound is liable to be a surplus. The components adhere firmly to the glass substrate, and removal of the excess after drying tends to be difficult. Therefore, a fluoroalkylsilane compound having a functional group capable of reacting with a silanol group at only one end is preferably used.
また、前記フルオロアルキルシラン系化合物の添加量は、撥水液の総量に対し、１〜２０質量％とすることが好ましい。１質量％未満では、初期撥水性（接触角）、耐候性および耐摩耗性が著しく低下する。また、２０質量％を超えると撥水液調合時の取り扱い性や撥水液のポットライフが悪くなるほか、撥水液が高コストとなるため、その添加量は、１〜２０質量％とすることが好ましい。 Further, the amount of the fluoroalkylsilane compound added is preferably 1 to 20% by mass with respect to the total amount of the water repellent liquid. If it is less than 1% by mass, the initial water repellency (contact angle), weather resistance and abrasion resistance are significantly reduced. On the other hand, if the amount exceeds 20% by mass, the handling property at the time of preparing the water repellent liquid and the pot life of the water repellent liquid become poor, and the cost of the water repellent liquid becomes high. Therefore, the addition amount is 1 to 20% by mass. It is preferable.
＜シロキサン化合物＞
本発明の撥水液に使用されるシロキサン化合物としては、一般式［２−１］又は一般式［２−２］で示されるシロキサン化合物の少なくとも１つが用いられる。
As the siloxane compound used in the water repellent liquid of the present invention, at least one of the siloxane compounds represented by the general formula [2-1] or the general formula [2-2] is used.
一般式［２−１］や一般式［２−２］で表されるシロキサン化合物は、ポリジメチルシロキサン（ＰＤＭＳ；一般式［３］で表される化合物）の側鎖にあるメチル基の一部が変性されたシロキサン化合物であり、一般式［１］で表されるフルオロアルキルシラン系化合物よりも表面エネルギーが高いため水分子との相互作用が小さく、また、分子骨格の柔軟性がより高いと考えられる。そのため、一般式［１］で表されるフルオロアルキルシラン系化合物のみを含む被膜よりも、該フルオロアルキルシラン系化合物と一般式［２−１］や一般式［２−２］で表されるシロキサン化合物とを重縮合させて得られた化合物を含む被膜のほうが、被膜表面の水滴を転がせやすくなり、滑水性を向上させることが出来たと発明者は推測している。
一般式［２−１］で表されるシロキサン化合物において、Ｙがアルコキシ基であることが好ましく、メトキシ基、エトキシ基及びプロポキシ基からなる群から選ばれる１つの基であることがより好ましい。また、ｂ／（ａ＋ｂ）は、０．０５〜０．３であることが好ましく、であることがより好ましく、０．０５〜０．２であることがさらに好ましい。ａは、通常１０〜５０であり、２０〜４０であることが好ましく、２５〜３５であることがより好ましい。ｂは、通常１〜１０であり、１〜５であることが好ましく、２〜４であることがより好ましい。 In the siloxane compound represented by the general formula [2-1], Y is preferably an alkoxy group, and more preferably one group selected from the group consisting of a methoxy group, an ethoxy group and a propoxy group. Further, b / (a + b) is preferably 0.05 to 0.3, more preferably, and further preferably 0.05 to 0.2. a is usually 10 to 50, preferably 20 to 40, and more preferably 25 to 35. b is usually 1 to 10, preferably 1 to 5, and more preferably 2 to 4.
一般式［２−２］で表されるシロキサン化合物において、Ｚがアルコキシ基であることが好ましく、メトキシ基、エトキシ基及びプロポキシ基からなる群から選ばれる１つの基であることがより好ましい。Ｒ１は、炭素原子数１〜４のアルキレン基であることが好ましく、炭素原子数２〜３のアルキレン基であることがより好ましい。Ｒ２は、それぞれ独立して炭素原子数１〜４のアルキル基であることが好ましく、それぞれ独立して炭素原子数１〜３のアルキル基であることがより好ましい。また、ｂ／（ａ＋ｂ）は、０．０５〜０．３であることが好ましく、０．０５〜０．２であることがより好ましい。ａは、通常１０〜５０であり、２０〜４０であることが好ましく、２５〜３５であることがより好ましい。ｂは、通常１〜１０であり、１〜５であることが好ましく、２〜４であることがより好ましい。 In the siloxane compound represented by the general formula [2-2], Z is preferably an alkoxy group, and more preferably one group selected from the group consisting of a methoxy group, an ethoxy group and a propoxy group. R 1 is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. R 2 is preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably independently an alkyl group having 1 to 3 carbon atoms. Further, b / (a + b) is preferably 0.05 to 0.3, and more preferably 0.05 to 0.2. a is usually 10 to 50, preferably 20 to 40, and more preferably 25 to 35. b is usually 1 to 10, preferably 1 to 5, and more preferably 2 to 4.
＜各材料の量比＞
本発明の撥水液においては、前記フルオロアルキルシラン系化合物と前記シロキサン化合物の質量比は通常１：１〜１：４であり、該質量比は１：１〜１：３であることが好ましく、１：２〜１：３であることがより好ましい。該質量比について、１：１よりも前記シロキサン化合物の割合が少ない場合は、滑水性を十分には得られにくく、１：４よりも前記シロキサン化合物の割合が多い場合は、撥水性を十分には得られにくい。
<Quantity ratio of each material>
In the water repellent liquid of the present invention, the mass ratio of the fluoroalkylsilane compound to the siloxane compound is usually 1: 1 to 1: 4, and the mass ratio is preferably 1: 1 to 1: 3. , 1: 2 to 1: 3 is more preferable. Regarding the mass ratio, when the ratio of the siloxane compound is less than 1: 1 it is difficult to obtain sufficient water sliding property, and when the ratio of the siloxane compound is more than 1: 4, the water repellency is sufficient. Is difficult to obtain.
＜有機溶媒＞
本発明の撥水液に用いる有機溶媒には、フルオロアルキルシラン系化合物、酸触媒を溶解させる有機溶媒を用いることができ、該有機溶媒として、エチルアルコール、イソプロピルアルコール等の低級アルコール、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸エチル、酢酸ブチル等のエステル類、ヘキサン、トルエン、ベンゼン、キシレン等の炭化水素溶媒類、ジエチルエーテル、ジイソプロピルエーテル等のエーテル類やそれらの混合物を用いることが好ましい。また、ハイドロフルオロカーボン、パーフルオロカーボン、パーフルオロエーテル、ハイドロフルオロエーテルなどのフッ素系溶剤を用いることもできる。中でも、イソプロピルアルコール等の低級アルコールは、フルオロアルキルシラン系化合物、酸触媒の溶解性が高く、さらに、撥水液の塗布性（塗り伸ばしやすさ）や乾燥時間（作業時間）が適度になるので特に好ましい。
<Organic solvent>
As the organic solvent used in the water repellent liquid of the present invention, a fluoroalkylsilane compound, an organic solvent capable of dissolving an acid catalyst can be used, and as the organic solvent, a lower alcohol such as ethyl alcohol or isopropyl alcohol, methyl ethyl ketone, methyl can be used. It is preferable to use ketones such as isobutyl ketone, esters such as ethyl acetate and butyl acetate, hydrocarbon solvents such as hexane, toluene, benzene and xylene, ethers such as diethyl ether and diisopropyl ether, and mixtures thereof. Further, a fluorinated solvent such as hydrofluorocarbon, perfluorocarbon, perfluoroether or hydrofluoroether can also be used. Among them, lower alcohols such as isopropyl alcohol have high solubility of fluoroalkylsilane compounds and acid catalysts, and moreover, coatability (ease of spreading) of water-repellent liquid and drying time (working time) are appropriate. Particularly preferred.
また、前記有機溶媒の添加量は、撥水液の総量に対し、８０〜９９質量％とすることが好ましく、９０〜９９質量％がより好ましい。８０質量％未満では、基材への撥水液の付着量が多くなりすぎ、撥水液の塗布性（塗り伸ばし易さ）が悪くなる。また、９９質量％を超えると基材への撥水液の付着量が少なくなり、撥水性や滑水性を十分には得にくい。 The amount of the organic solvent added is preferably 80 to 99% by mass, more preferably 90 to 99% by mass, based on the total amount of the water repellent liquid. If it is less than 80% by mass, the amount of the water-repellent liquid adhered to the substrate becomes too large, and the coating property of the water-repellent liquid (ease of spreading) becomes poor. On the other hand, if it exceeds 99% by mass, the amount of the water-repellent liquid attached to the base material will be small, and it will be difficult to obtain sufficient water repellency and water sliding property.
＜水＞
本発明の撥水液に用いる水は、該フルオロアルキルシラン系化合物と前記シロキサン化合物とを少なくとも部分的に加水分解、重縮合反応を生じさせるための成分である。前記水の添加量は、前記フルオロアルキルシラン系化合物のモル数と前記シロキサン化合物のモル数の合計の０．１〜１３０倍のモル数とすることが好ましく、３〜３０倍がより好ましい。０．１倍未満では、撥水液中で加水分解、重縮合反応が進行しにくく、基材に十分量の前記フルオロアルキルシラン系化合物や前記シロキサン化合物が接着しにくいため、撥水性や滑水性を十分には得にくい。また、１３０倍を超えると、撥水液中で加水分解、重縮合反応が進行しすぎて、ポットライフが短くなりやすい。また、撥水液中の含有水分量を調整するために、撥水液に脱水剤を添加し、所定時間脱水処理を行っても良い。脱水剤としては、シリカゲル、合成ゼオライト、活性アルミナ等を用いることが出来るが、これに限定するものではない。
<Water>
Water used for the water repellent liquid of the present invention is a component for causing at least partial hydrolysis and polycondensation reaction of the fluoroalkylsilane compound and the siloxane compound. The amount of water added is preferably 0.1 to 130 times, and more preferably 3 to 30 times, the total number of moles of the fluoroalkylsilane compound and the siloxane compound. If it is less than 0.1 times, the hydrolysis and polycondensation reaction in the water-repellent liquid is unlikely to proceed, and a sufficient amount of the fluoroalkylsilane compound or the siloxane compound is unlikely to adhere to the substrate, resulting in water repellency or water sliding property. Is hard to get enough. On the other hand, when it exceeds 130 times, hydrolysis and polycondensation reaction proceed excessively in the water repellent liquid, and the pot life tends to be shortened. Further, in order to adjust the amount of water contained in the water repellent liquid, a dehydrating agent may be added to the water repellent liquid and dehydration treatment may be performed for a predetermined time. As the dehydrating agent, silica gel, synthetic zeolite, activated alumina and the like can be used, but the dehydrating agent is not limited to these.
＜酸＞
本発明の撥水液に用いる酸は、前記フルオロアルキルシラン系化合物及び前記シロキサン化合物の重縮合反応を促進するための成分であり、無機酸、有機酸のいずれも用いることができる。酸の中では、有機スルホン酸が、撥水性被膜の耐摩耗性を良好にしやすいため好ましい。
<Acid>
The acid used in the water repellent liquid of the present invention is a component for promoting the polycondensation reaction of the fluoroalkylsilane compound and the siloxane compound, and either an inorganic acid or an organic acid can be used. Among the acids, organic sulfonic acids are preferable because they easily improve the wear resistance of the water-repellent coating.
撥水液に用いる有機スルホン酸としては、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、２−プロパンスルホン酸、ブタンスルホン酸、２−ブタンスルホン酸、ノナフルオロ−１−ブタンスルホン酸、ペンタンスルホン酸、トリフルオロメタンスルホン酸、２−ヒドロキシエタン−１−スルホン酸、２−ヒドロキシプロパン−１−スルホン酸、２−ヒドロキシブタン−１−スルホン酸、２−ヒドロキシペンタンスルホン酸、１−カルボキシエタンスルホン酸、１，３−プロパンジスルホン酸、アリールスルホン酸、２−スルホ酢酸、２−又は３−スルホプロピオン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、キシレンスルホン酸、ニトロベンゼンスルホン酸、スルホ安息香酸、スルホサリチル酸、ベンズアルデヒドスルホン酸、ｐ−フェノールスルホン酸、フェノール−２，４−ジスルホン酸などが挙げられる。中でもメタンスルホン酸、エタンスルホン酸やｐ−トルエンスルホン酸は容易に入手でき、さらに安全性（揮発しにくい）や取り扱い（吸湿しにくい）の観点から特に好ましい。 Examples of the organic sulfonic acid used in the water repellent liquid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, butanesulfonic acid, 2-butanesulfonic acid, nonafluoro-1-butanesulfonic acid, pentanesulfonic acid. , Trifluoromethanesulfonic acid, 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentanesulfonic acid, 1-carboxyethanesulfonic acid, 1,3-propanedisulfonic acid, arylsulfonic acid, 2-sulfoacetic acid, 2- or 3-sulfopropionic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, nitrobenzenesulfonic acid, sulfobenzoic acid, sulfosalicylic acid , Benzaldehyde Acid, p- phenolsulfonic acid, phenol-2,4-disulfonic acid. Among them, methanesulfonic acid, ethanesulfonic acid and p-toluenesulfonic acid are easily available, and are particularly preferable from the viewpoint of safety (hard to volatilize) and handling (hard to absorb moisture).
また、前記酸の添加量は、前記フルオロアルキルシラン系化合物のモル数と前記ケイ素化合物のモル数の合計の０．１〜１３倍のモル数とすることが好ましく、０．１〜７倍のモル数がさらに好ましい。０．１倍未満では、撥水液中で重縮合反応が進行しにくく、基材に十分量の前記フルオロアルキルシラン系化合物や前記ケイ素化合物が接着しにくいため、撥水性や滑水性を十分には得にくい。また、１３倍を超えると、撥水液中で重縮合反応が進行しすぎて、ポットライフが短くなりやすい。 Further, the addition amount of the acid is preferably 0.1 to 13 times, and preferably 0.1 to 7 times, the total number of moles of the fluoroalkylsilane compound and the silicon compound. More preferred is the number of moles. If it is less than 0.1 times, the polycondensation reaction is difficult to proceed in the water repellent liquid, and the sufficient amount of the fluoroalkylsilane compound or the silicon compound is hard to adhere to the substrate, so that the water repellency and the water sliding property are sufficient. Is hard to get. If it exceeds 13 times, the polycondensation reaction proceeds too much in the water repellent liquid, and the pot life tends to be shortened.
＜撥水液の調製方法＞
次に本発明の撥水液の好ましい調製方法について説明する。
撥水液は、一般式［１］で表される前記フルオロアルキルシラン系化合物、一般式［２−１］又は［２−２］で表されるシロキサン化合物、有機溶媒の混合物に、水及び酸を添加、混合し、該フルオロアルキルシラン系化合物や該シロキサン化合物を重縮合することにより得られる。ここで、該フルオロアルキルシラン系化合物、該シロキサン化合物、有機溶媒を先に混合するのは、該フルオロアルキルシラン系化合物と該シロキサン化合物を撥水液中に均質に混合させるためである。しかしながら、上記の原料を同時に混合しても良い。
<Method for preparing water repellent liquid>
Next, a preferred method for preparing the water repellent liquid of the present invention will be described.
The water-repellent liquid is a mixture of the fluoroalkylsilane compound represented by the general formula [1], the siloxane compound represented by the general formula [2-1] or [2-2], an organic solvent, water and an acid. Can be obtained by polycondensing the fluoroalkylsilane compound and the siloxane compound. Here, the reason why the fluoroalkylsilane compound, the siloxane compound, and the organic solvent are mixed first is to uniformly mix the fluoroalkylsilane compound and the siloxane compound in the water repellent liquid. However, the above raw materials may be mixed at the same time.
＜撥水性物品の製造方法＞
次に、得られた撥水液を使用して、撥水性物品を製造する方法について説明する。
上記で得られた撥水液を基材表面に塗布する塗布方法としては、手塗り法、ノズルフローコート法、ディッピング法、スプレー法、リバースコート法、フレキソ法、印刷法、フローコート法、スピンコート法、ロールコート法、それらの併用等各種塗布方法が適宜採用され得る。これらの塗布方法の中では、手塗り法が、塗着効率が高く塗布ロスが少ない点、塗布設備の導入費用を削減できる点、透明性に優れ、キズが目立ちにくい、ｎｍオーダーの膜厚の被膜を形成できる点などから好ましい。なお、本発明で「手塗り法」とは、塗布液を部材に給液した後、該部材を基材に接触させる手段、及び、塗布液を基材に給液した後、部材で該塗布液を引き延ばす手段から選ばれる少なくとも一つの手段で基材上に塗布液を塗布する技術手段のことを指す。塗布液を給液される部材、又は塗布液を引き延ばす部材としては、布、紙、不織布、ガーゼ、スポンジ、フェルトなどが挙げられる。塗布液を給液された部材を基材に接触させる手段、又は部材で塗布液を引き延ばす手段は、人の手によるもの、ロボットや機械などによるものなどがある。
<Method for manufacturing water-repellent article>
Next, a method for producing a water repellent article using the obtained water repellent liquid will be described.
As a coating method for coating the substrate surface with the water repellent liquid obtained above, a hand coating method, a nozzle flow coating method, a dipping method, a spray method, a reverse coating method, a flexographic method, a printing method, a flow coating method, a spin coating method. Various coating methods such as a coating method, a roll coating method and a combination thereof can be appropriately adopted. Among these coating methods, the hand coating method has a high coating efficiency and a small coating loss, the cost of introducing coating equipment can be reduced, the transparency is excellent, and scratches are not noticeable. It is preferable from the viewpoint that a film can be formed. In the present invention, the "hand-coating method" means means for supplying a coating liquid to a member and then bringing the member into contact with a base material, and after supplying the coating liquid to the base material, applying the coating liquid on the member. It means a technical means for applying a coating liquid onto a substrate by at least one means selected from means for spreading the liquid. Examples of the member to which the coating liquid is supplied or the member to spread the coating liquid include cloth, paper, non-woven fabric, gauze, sponge and felt. The means for bringing the member supplied with the coating liquid into contact with the substrate or the means for spreading the coating liquid by the member include those by human hands, those by robots or machines, and the like.
本発明の撥水性物品の製造方法は、塗布後に５０〜３５０℃で１〜６０分間加熱を行うことが好ましいが、その加熱温度よりも高い耐熱温度を有するものであれば、撥水液が塗布される基材は特に限定されるものではない。例えば、車両用窓ガラス、建築物用窓ガラスに通常使用されているフロート板ガラス、又はロールアウト法で製造されたソーダ石灰ガラス等無機質の透明性がある板ガラスを使用できる。これら板ガラスを用いて形成される鏡等の反射性基材、擦りガラス、模様が刻まれたガラス等の半透明から不透明のガラス基材を使用することができる。 In the method for producing a water-repellent article of the present invention, it is preferable to carry out heating at 50 to 350 ° C. for 1 to 60 minutes after coating, but a water repellent liquid is coated as long as it has a heat resistant temperature higher than the heating temperature. The substrate to be used is not particularly limited. For example, it is possible to use a glass sheet having an inorganic transparency such as a window glass for a vehicle, a float glass sheet usually used for a building window glass, or a soda lime glass produced by a roll-out method. A reflective base material such as a mirror formed by using these plate glasses, a translucent to opaque glass base material such as frosted glass or glass having a pattern engraved thereon can be used.
前記ガラス基材の他にタイル、瓦、衛生陶器、食器等に使用されるセラミックス材料よりなる基材、ガラス窓等の枠体、調理器、メス、注射針等の医療器具、流し、自動車のボディ等に使用されるステンレス鋼、アルミニウム、鉄鋼等の金属材料、プラスチック製の基材、例えば、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリメチルメタアクリレート樹脂、ポリエチレン樹脂、ポリ塩化ビニル樹脂、その他のプラスチック基材を使用することがある。 In addition to the glass base material, a base material made of a ceramic material used for tiles, roof tiles, sanitary ware, tableware, etc., a frame body such as a glass window, a cooker, a medical instrument such as a scalpel and an injection needle, a sink, an automobile Metallic materials such as stainless steel, aluminum, steel, etc. used for body etc., plastic base materials such as polycarbonate resin, polyethylene terephthalate resin, polymethylmethacrylate resin, polyethylene resin, polyvinyl chloride resin, and other plastic base materials Material may be used.
また、基材と撥水性被膜との接着強度を向上させる処理を基材表面に予め行うこともできる。前記の処理としては、各種研磨液による研磨・洗浄・乾燥、酸性溶液または塩基性溶液による表面改質処理、プライマー処理、プラズマ照射、コロナ放電、高圧水銀灯照射等により、基材表面に活性基を発生させることが挙げられる。特に、プライマー処理は、例えば基材上に官能基を４個有するケイ素化合物が添加された溶液を基材に塗布し、該ケイ素化合物と基材とを結合させるとともに、該ケイ素化合物由来のシラノール基（活性基）を形成させて行うことができ、撥水液を塗布する表面のシラノール基の数を増やすことができるため好ましい。 Further, the surface of the base material can be previously treated to improve the adhesive strength between the base material and the water-repellent coating. Examples of the treatment include polishing / washing / drying with various polishing liquids, surface modification treatment with an acidic solution or basic solution, primer treatment, plasma irradiation, corona discharge, high pressure mercury lamp irradiation, etc. It can be generated. Particularly, in the primer treatment, for example, a solution in which a silicon compound having four functional groups is added to the base material is applied to the base material to bond the silicon compound and the base material together with a silanol group derived from the silicon compound. (Active group) can be formed, and the number of silanol groups on the surface to which the water repellent liquid is applied can be increased, which is preferable.
次に撥水液を基材に塗布した後の処理について説明する。基材に撥水液を塗布後、５０〜３５０℃で１〜６０分間加熱させることが好ましい。前記フルオロアルキルシラン系化合物のＸに由来するシラノール基と、基材表面に存在する水酸基等の結合性基とを、加熱処理を行わなかった場合よりもより強く結合させることにより、該基材表面に優れた耐久性、特に耐候性、耐摩耗性を両立する固形の被膜（撥水層）を形成することができる。加熱は、常圧下、加圧下、減圧下、不活性雰囲気下で行っても良い。 Next, the treatment after applying the water repellent liquid to the substrate will be described. After applying the water-repellent liquid to the substrate, it is preferable to heat the substrate at 50 to 350 ° C. for 1 to 60 minutes. By binding the silanol group derived from X of the fluoroalkylsilane compound and a bonding group such as a hydroxyl group existing on the surface of the base material more strongly than in the case where heat treatment is not carried out, the base material surface It is possible to form a solid coating (water-repellent layer) having excellent durability, particularly weather resistance and abrasion resistance. The heating may be performed under normal pressure, increased pressure, reduced pressure, or an inert atmosphere.
最後に、余剰分が乾固物となって基材上に残留するので、この余剰分を有機溶剤で湿らした紙タオルや布および／または乾いた紙タオルや布で払拭することにより撥水性被膜が形成された物品が得られる。 Finally, since the surplus becomes a dry solid and remains on the substrate, the surplus is wiped with a paper towel or cloth moistened with an organic solvent and / or a dry paper towel or cloth to form a water-repellent film. An article in which is formed is obtained.
これらの製造工程により、基材と、該基材上に撥水性被膜の形成された撥水性物品であって、該撥水性被膜が、前記一般式［１］で表されるフルオロアルキルシラン系化合物と、前記一般式［２−１］又は［２−２］で表されるシロキサン化合物の少なくとも１つとの部分加水分解重縮合物を含む撥水性被膜である撥水性物品を得られる。 A water-repellent article having a substrate and a water-repellent coating formed on the substrate by these manufacturing steps, wherein the water-repellent coating is a fluoroalkylsilane compound represented by the general formula [1]. And a water-repellent article containing a partially hydrolyzed polycondensate of at least one of the siloxane compounds represented by the general formula [2-1] or [2-2].
実施例により本発明を具体的に説明する。本実施例および比較例で得られた撥水性物品は、以下に示す方法により品質評価を行った。本実施例および比較例で作製した撥水性物品は、ガラス基板の片側の全面に撥水性被膜を形成した構成である。なお、本発明はこれらの実施例に限定されるものではない。 The present invention will be specifically described with reference to examples. The water-repellent articles obtained in this example and the comparative example were quality-evaluated by the following method. The water-repellent articles manufactured in this example and the comparative example have a structure in which a water-repellent coating is formed on the entire surface of one side of the glass substrate. The present invention is not limited to these examples.
［外観］
撥水性物品の外観を目視にて確認し、撥水性被膜に膜ムラ、クラック、着色などの外観上の不具合がないものを合格（○）、外観上の不具合があるものを不合格（×）とした。
[appearance]
Visually check the appearance of the water-repellent article, and pass if the water-repellent coating has no appearance defects such as film unevenness, cracks, or coloring (○), and if it has any external appearance defects (x). And
［撥水性物品の接触角；撥水性］
撥水性物品の撥水層表面に、純水約２μｌを置いたときの水滴とサンプル表面とのなす角を接触角計で測定した。尚、接触角計には協和界面科学製ＤＭ−５０１型を用い、大気中（約２５℃）で測定した。初期接触角において、接触角が１０５°以上を合格（表中で○と表記）、１０５°未満を性能不足とし、不合格（表中で×と表記）とした。
[Contact angle of water repellent article; water repellency]
The angle formed between the water droplet and the sample surface when approximately 2 μl of pure water was placed on the surface of the water repellent layer of the water repellent article was measured with a contact angle meter. A contact angle meter DM-501 manufactured by Kyowa Interface Science Co., Ltd. was used, and measurement was performed in the atmosphere (about 25 ° C.). Regarding the initial contact angle, a contact angle of 105 ° or more was passed (indicated by O in the table), and a contact angle of less than 105 ° was regarded as insufficient performance, and was rejected (indicated by X in the table).
［撥水性物品の転落角；滑水性］
サンプルを水平に保持した状態で、サンプル表面上に５０μｌの純水を滴下した後、サンプルを徐々に傾けていき、水滴が移動し始めた時点の傾斜角度を転落角（°）とした。尚、転落角は協和界面科学製ＤＭ−５０１型を用いて大気中（約２５℃）で測定した。転落角が小さいほど滑水性が良好であるといえ、転落角の初期性能が、１５°以下を合格（表中で○と表記）、１６°以上を性能不足とし、不合格（表中で×と表記）とした。
[Falling angle of water-repellent article; water sliding property]
With the sample held horizontally, 50 μl of pure water was dropped on the sample surface, the sample was gradually tilted, and the inclination angle at the time when the water droplet started to move was defined as the falling angle (°). The fall angle was measured in the atmosphere (about 25 ° C.) using DM-501 manufactured by Kyowa Interface Science. It can be said that the smaller the sliding angle is, the better the water sliding property is, and the initial performance of the sliding angle is 15 ° or less (passed in the table), 16 ° or more is insufficient performance, and fails (x in the table). And notation).
［撥水性物品の耐摩耗性］
以下の条件で、トラバース試験を実施した後の転落角（°）を測定して評価した。ここでは、試験後の水滴の転落角が２０°以下を合格（表中で○と表記）、２１°以上を性能不足とし、不合格（表中で×と表記）とした。
・ 試験機 ：トラバ−ス式摺動試験機
・ 試料サイズ ：約２００ｍｍ×２００ｍｍ
・ 摩擦子 ：ネル布
・ 荷重 ：３００ｇ／ｃｍ２
・ ストロ−ク ：１５００往復
・ 摺動速度 ：４０往復／分
[Abrasion resistance of water repellent articles]
Under the following conditions, the sliding angle (°) after carrying out the traverse test was measured and evaluated. Here, the water drop angle after the test was 20 ° or less (passed in the table), and 21 ° or more was insufficient, and the performance was unacceptable (indicated as x in the table).
・ Testing machine: Traverse type sliding tester ・ Sample size: Approx. 200 mm x 200 mm
・ Friction element: flannel cloth
・ Load: 300 g / cm 2
・ Stroke: 1500 reciprocations ・ Sliding speed: 40 reciprocations / min
［実施例１］
（シロキサン化合物Ａの合成）
トルエン；５．８ｇ、ビニルジメチルエトキシシラン；０．８ｇ、３％−ＰＴ−ＶＴＳ−ＩＰＡ溶液（ジビニルテトラメチルジシロキサン白金錯体イソプロピルアルコール溶液）；１００μＬ、ＰＤＭＳの側鎖にあるメチル基の一部が水素原子に変性されたシロキサン化合物〔以下、側鎖Ｈ−変性ＰＤＭＳとも言う、構造式［４］、数平均分子量：２，５００）〕；５．０ｇを添加し、窒素雰囲気にて、１００℃で３時間撹拌後、イソプロピルアルコールで希釈し、固形分濃度４ｗｔ％のシロキサン化合物Ａを得た。
(Synthesis of Siloxane Compound A)
Toluene: 5.8 g, vinyldimethylethoxysilane: 0.8 g, 3% -PT-VTS-IPA solution (divinyltetramethyldisiloxane platinum complex isopropyl alcohol solution): 100 μL, part of the methyl group in the side chain of PDMS Is a hydrogen atom-modified siloxane compound [hereinafter also referred to as side chain H-modified PDMS, structural formula [4], number average molecular weight: 2,500); After stirring at ℃ for 3 hours, it was diluted with isopropyl alcohol to obtain a siloxane compound A having a solid content concentration of 4 wt%.
（１Ｈ−ＮＭＲによる合成物の確認）
減圧乾燥により、濃縮したシロキサン化合物Ａの１Ｈ−ＮＭＲ分析を行った。測定は、該シロキサン化合物Ａ：５ｍｇと重水素化クロロホルム：４ｍｌを採取、混合して行った。結果、Ｓｉ−ＣＨ３（０ｐｐｍ）、Ｓｉ−ＣＨ２−ＣＨ２−（０．４〜０．６ｐｐｍ）、−ＯＣＨ２−ＣＨ３（１．２、３．６ｐｐｍ）のピークが得られたことより、式［５］で表されるシロキサン化合物が合成出来ていることを確認した（図１のスペクトル参照）。
By vacuum drying, it was subjected to 1 H-NMR analysis of the concentrated siloxane compound A. The measurement was performed by collecting and mixing 5 mg of the siloxane compound A and 4 ml of deuterated chloroform. As a result, peaks of Si—CH 3 (0 ppm), Si—CH 2 —CH 2 — (0.4 to 0.6 ppm), and —OCH 2 —CH 3 (1.2, 3.6 ppm) were obtained. From this, it was confirmed that the siloxane compound represented by the formula [5] could be synthesized (see the spectrum in FIG. 1).
（塗布液の調製）
フルオロカーボンユニットの数が６のフルオロアルキルシラン化合物〔ＣＦ３（ＣＦ２）５ＣＨ２ＣＨ２Ｓｉ（ＯＣ2Ｈ5）３〕；１．０ｇ、シロキサン化合物Ａ（固形分濃度；４ｗｔ％）；５０．０ｇ、イソプロピルアルコール；２２．４ｇを混合し、約５分間攪拌した。次いで、メタンスルホン酸０．９４ｇ、水；０．７１ｇを添加し、室温で２時間攪拌して、該フルオロアルキルシラン化合物とシロキサン化合物Ａの質量比が１：２、固形分濃度；４ｗｔ％の塗布液を得た。
(Preparation of coating liquid)
Fluoroalkyl silane compound having a fluorocarbon units 6 [CF 3 (CF 2) 5 CH 2 CH 2 Si (OC 2 H 5) 3 ]; 1.0 g, siloxane compound A (solids concentration; 4wt%); 50 2.0 g and isopropyl alcohol; 22.4 g were mixed and stirred for about 5 minutes. Next, 0.94 g of methanesulfonic acid and 0.71 g of water were added, and the mixture was stirred at room temperature for 2 hours, the mass ratio of the fluoroalkylsilane compound and the siloxane compound A was 1: 2, and the solid content concentration was 4 wt%. A coating liquid was obtained.
（基材の準備）
１０ｃｍ角で厚さ３．０ｍｍのフロートガラス板の表面を酸化セリウムで十分に研磨した後、精製水で洗浄後、乾燥させて基材を準備した。
(Preparation of base material)
The surface of a 10 cm square float glass plate having a thickness of 3.0 mm was sufficiently polished with cerium oxide, washed with purified water, and then dried to prepare a substrate.
（撥水性物品の作製）
調製した塗布液１．０ｍｌをガラス基板上に滴下し、綿布（商品名；ベンコット）でガラス全面に十分引き伸ばした後、５分程度風乾した。その後、ガラスを電気炉に入れ１０分間熱処理した。このとき、ガラスの最高温度（熱処理温度）は１５０℃であった。最後に、目視で白くまだらに残留している余剰な撥水成分をイソプロピルアルコールで湿らした紙タオルで拭き上げて、目視観察で問題の無い透明なサンプルを得た。
(Preparation of water repellent article)
1.0 ml of the prepared coating solution was dropped on a glass substrate, sufficiently spread over the entire surface of the glass with a cotton cloth (trade name: Bemcot), and then air-dried for about 5 minutes. Then, the glass was placed in an electric furnace and heat-treated for 10 minutes. At this time, the maximum temperature (heat treatment temperature) of the glass was 150 ° C. Finally, the excess water-repellent component that remained white and mottled with the naked eye was wiped off with a paper towel moistened with isopropyl alcohol, and a transparent sample with no problem was obtained by visual observation.
上記の評価方法に記載した要領で評価したところ、表１に示すとおり、転落角：○（１５°）、接触角：○（１０８°）、耐摩耗性：○（１８°）であり、優れた転落角を有していた。また、接触角、耐摩耗性も良好であった。 When evaluated according to the procedure described in the above evaluation method, as shown in Table 1, the sliding angle is ◯ (15 °), the contact angle is ◯ (108 °), and the wear resistance is ◯ (18 °), which is excellent. Had a fall angle. The contact angle and wear resistance were also good.
［実施例２〜５、比較例１〜２７］
表１に示すとおり、フルオロアルキルシラン系化合物の添加の有無、シロキサン化合物の種類や分子量、フルオロアルキルシラン系化合物とシロキサン化合物の質量比を変え、それ以外は実施例１と同様に実施した。以下に、一部のシロキサン化合物の合成方法、入手方法について説明する。
[Examples 2 to 5, Comparative Examples 1 to 27]
As shown in Table 1, the same procedure as in Example 1 was carried out except that the addition or non-addition of the fluoroalkylsilane compound, the type and molecular weight of the siloxane compound, and the mass ratio of the fluoroalkylsilane compound and the siloxane compound were changed. Below, the synthetic | combination method of some siloxane compounds and the acquisition method are demonstrated.
（シロキサン化合物Ｂの合成：実施例２、３で使用）
エタノール；１０ｇ、３％−ＰＴ−ＶＴＳ−ＩＰＡ溶液（ジビニルテトラメチルジシロキサン白金錯体イソプロピルアルコール 溶液）；１００μＬ、側鎖Ｈ−変性ＰＤＭＳ［構造式［４］、数平均分子量：２，５００〕；９ｇを添加し、窒素雰囲気にて、７０℃で１８時間撹拌後、イソプロピルアルコールで希釈し、固形分濃度４ｗｔ％のシロキサン化合物Ｂを得た。実施例１と同様に、シロキサン化合物Ｂの１Ｈ−ＮＭＲ分析を行い、式［６］で表されるシロキサン化合物が合成出来ていることを確認した。
Ethanol; 10 g, 3% -PT-VTS-IPA solution (divinyltetramethyldisiloxane platinum complex isopropyl alcohol solution); 100 μL, side chain H-modified PDMS [structural formula [4], number average molecular weight: 2,500]; 9 g was added, the mixture was stirred at 70 ° C. for 18 hours in a nitrogen atmosphere, and then diluted with isopropyl alcohol to obtain a siloxane compound B having a solid content concentration of 4 wt%. 1 H-NMR analysis of the siloxane compound B was performed in the same manner as in Example 1, and it was confirmed that the siloxane compound represented by the formula [6] could be synthesized.
（シロキサン化合物Ｃの合成：実施例４、５で使用）
イソプロピルアルコール；２４．９ｇ、０．５ＮのＮａＯＨ；０．１ｇ、側鎖Ｈ−変性ＰＤＭＳ［構造式［４］、数平均分子量：２，５００〕；１ｇを添加し、室温で３時間撹拌して、固形分濃度；４ｗｔ％のシロキサン化合物Ｃを得た。実施例１と同様に、シロキサン化合物Ｃの１Ｈ−ＮＭＲ分析を行い、式［７］で表されるシロキサン化合物が合成出来ていることを確認した。
14.9 g of isopropyl alcohol; 24.9 g, 0.5 N NaOH; 0.1 g, side chain H-modified PDMS [structural formula [4], number average molecular weight: 2,500], and the mixture was stirred at room temperature for 3 hours. Thus, a siloxane compound C having a solid content concentration of 4 wt% was obtained. In the same manner as in Example 1, 1 H-NMR analysis of the siloxane compound C was performed, and it was confirmed that the siloxane compound represented by the formula [7] could be synthesized.
（シロキサン化合物Ｄ、Ｅ：比較例２、３で使用）
比較例２では、シロキサン化合物Ｄとして、構造式［８］で表されるシロキサン化合物（ｎ＝５０、製品名ＫＦ−８５７、信越化学工業）を用いた。
比較例３では、シロキサン化合物Ｅとして、構造式［８］で表されるシロキサン化合物（ｎ＝２７０、製品名ＫＦ−８６２、信越化学工業）を用いた。
In Comparative Example 2, a siloxane compound represented by the structural formula [8] (n = 50, product name KF-857, Shin-Etsu Chemical Co., Ltd.) was used as the siloxane compound D.
In Comparative Example 3, as the siloxane compound E, a siloxane compound represented by the structural formula [8] (n = 270, product name KF-862, Shin-Etsu Chemical Co., Ltd.) was used.
（シロキサン化合物Ｆ、Ｇ：比較例４、５で使用）
比較例４では、シロキサン化合物Ｄとして、構造式［９］で表されるシロキサン化合物（ｎ＝４０、製品名ＫＦ−９７０１、信越化学工業）を用いた。
比較例５では、シロキサン化合物Ｅとして、構造式［９］で表されるシロキサン化合物（ｎ＝２０、製品名Ｘ−２１−５８４１、信越化学工業）を用いた。
In Comparative Example 4, a siloxane compound represented by the structural formula [9] (n = 40, product name KF-9701, Shin-Etsu Chemical Co., Ltd.) was used as the siloxane compound D.
In Comparative Example 5, as the siloxane compound E, a siloxane compound represented by the structural formula [9] (n = 20, product name X-21-5841, Shin-Etsu Chemical Co., Ltd.) was used.
各実施例及び各比較例について、撥水液の各成分とその割合を表１に示す。また、各実施例及び各比較例で得られた撥水性物品に関し、外観の観察結果、転落角、初期の水接触角、耐摩耗性の測定結果も下記の表１に示す。 Table 1 shows each component of the water repellent liquid and its ratio for each example and each comparative example. Further, with respect to the water-repellent articles obtained in each of the examples and each of the comparative examples, the observation results of the appearance, the falling angle, the initial water contact angle, and the abrasion resistance measurement results are also shown in Table 1 below.
［表１］
[Table 1]
表１より明らかなように、実施例１〜５では、撥水液は、一般式［１］で表されるフルオロアルキルシラン系化合物、一般式［２−１］又は［２−２］で表されるシロキサン化合物の少なくとも１つ、有機溶媒、水、及び、酸を含み、該フルオロアルキルシラン系化合物と該シロキサン化合物の質量比が１：１〜１：４の撥水液であり、該撥水液を用いて製造した撥水性物品は、滑水性が良好であった。さらに、該撥水性物品の外観、初期の接触角、耐摩耗性も良好であった。 As is clear from Table 1, in Examples 1 to 5, the water-repellent liquid was a fluoroalkylsilane compound represented by the general formula [1] or a general formula [2-1] or [2-2]. At least one of the siloxane compounds, an organic solvent, water, and an acid, wherein the mass ratio of the fluoroalkylsilane compound to the siloxane compound is 1: 1 to 1: 4. The water-repellent article produced by using the water solution had good water sliding property. Further, the appearance, initial contact angle, and abrasion resistance of the water-repellent article were also good.
特に、実施例４では、材料として使用しているシロキサン化合物Ｃは、室温撹拌にて合成可能であり、また、得られる撥水性物品も転落角１４°、接触角１０７°であり、滑水性と撥水性のバランスに優れていた。 In particular, in Example 4, the siloxane compound C used as a material can be synthesized by stirring at room temperature, and the resulting water-repellent article also has a falling angle of 14 ° and a contact angle of 107 °, and is It had an excellent balance of water repellency.
［比較例１〜５］
一般式［２−１］又は［２−２］で表されるシロキサン化合物の代わりに、変性部位の無いＰＤＭＳや、側鎖にシラノール基やアルコキシ基を有さない変性ＰＤＭＳを用いたところ、実施例よりも転落角が大きく、滑水性が劣っていた。
[Comparative Examples 1 to 5]
Instead of the siloxane compound represented by the general formula [2-1] or [2-2], PDMS having no modification site or modified PDMS having no silanol group or alkoxy group in the side chain was used. The sliding angle was larger than that of the example, and the water sliding property was inferior.
［比較例６〜１１］
一般式［２−１］又は［２−２］で表されるシロキサン化合物の代わりに、シロキサン化合物の変性部位中の活性基（反応性基）数が多い変性ＰＤＭＳを用いた場合、撥水液及び撥水性被膜に白濁が生じたり、滑水性が実施例よりも劣ったりしていた。
[Comparative Examples 6 to 11]
When a modified PDMS having a large number of active groups (reactive groups) in the modified site of the siloxane compound is used instead of the siloxane compound represented by the general formula [2-1] or [2-2], a water repellent liquid. In addition, the water-repellent coating was clouded, and the water sliding property was inferior to that in Examples.
［比較例１２〜１７］
b/(a+b)が大きい場合、撥水液及び撥水性被膜に白濁が生じたり、実施例より滑水性が劣ったりしていた。
[Comparative Examples 12 to 17]
When b / (a + b) was large, the water-repellent liquid and the water-repellent coating were clouded, and the water sliding property was inferior to that in Examples.
［比較例１８〜２３］
フルオロアルキルシラン系化合物の割合が多い場合、実施例よりも滑水性が劣り、シロキサン化合物の割合が多い場合、撥水性が不十分であった。
[Comparative Examples 18 to 23]
When the ratio of the fluoroalkylsilane compound was large, the water sliding property was inferior to that of the example, and when the ratio of the siloxane compound was large, the water repellency was insufficient.
［比較例２４〜２７］
フルオロアルキルシラン系化合物又はシロキサン化合物の一方を欠く場合、実施例よりも滑水性又は撥水性が劣っていた。
[Comparative Examples 24 to 27]
When either the fluoroalkylsilane compound or the siloxane compound was lacking, the water sliding property or water repellency was inferior to that of the examples.
撥水性を有する撥水ガラスは、雨天時、雨滴をはじくため、室内から室外への良好な視界が保たれる。このため、撥水ガラスは、建築、車両、船舶、航空機など種々の分野にて、使用されている。特に、水滴が滑りやすい滑水性の優れた撥水ガラスは、雨滴除去性が良好なため、雨天運転時の安全性が格段に向上する。このため、実使用に耐えうる耐久性を有する滑水性の優れた撥水ガラスが望まれている。また、滑水性の優れた撥水性材料は、着氷、着雪を低減させる効果も有しているため、豪雪地域の電線や屋外アンテナ向けの撥水性物品としても期待されている。 The water-repellent glass, which has water repellency, repels raindrops in the case of rain, so that a good visibility from the inside to the outside can be maintained. For this reason, water-repellent glass is used in various fields such as construction, vehicles, ships, and aircraft. In particular, the water-repellent glass, which has excellent water-sliding property in which water droplets are slippery, has a good raindrop removal property, so that the safety during rainy operation is significantly improved. Therefore, a water-repellent glass having excellent durability and durability that can withstand actual use is desired. Further, since the water-repellent material having excellent water-sliding property also has an effect of reducing ice accretion and snow accretion, it is expected as a water-repellent article for electric wires and outdoor antennas in heavy snowfall areas.
車両用の窓ガラスは、フロントウインドウやバックウインドウに取り付けられているワイパーブレードとの摩耗や、サイドドアガラスに取り付けられている水切りモールとの昇降時の摩耗に耐えうる必要がある。また、建築用の窓ガラスは、タオルなどを用いた清掃による払拭に耐えうる必要がある。 A window glass for a vehicle needs to be able to withstand abrasion with a wiper blade attached to a front window or a back window, and abrasion with a draining molding attached to a side door glass when moving up and down. Further, the window glass for construction needs to be able to withstand wiping by cleaning with a towel or the like.
本発明の撥水性物品は、滑水性が良好であり、車両用の窓ガラスや建築用の窓ガラスとして用いることが出来る。 The water-repellent article of the present invention has good water sliding property and can be used as a window glass for vehicles or a window glass for construction.
Claims (16)
一般式［２−１］又は一般式［２−２］で表されるシロキサン化合物の少なくとも１つ、
有機溶媒、水、及び、酸
を含み、該フルオロアルキルシラン系化合物と該シロキサン化合物の質量比が１：１〜１：４である、撥水性被膜を形成するための撥水液。
At least one siloxane compound represented by the general formula [2-1] or the general formula [2-2],
A water-repellent liquid for forming a water-repellent coating film, which contains an organic solvent, water, and an acid, and has a mass ratio of the fluoroalkylsilane compound to the siloxane compound of 1: 1 to 1: 4.
一般式［２−１−Ａ］で表されるシロキサン化合物、
有機溶媒、水、及び、酸
を含み、該フルオロアルキルシラン系化合物と該シロキサン化合物の質量比が１：２〜１：３である、撥水性被膜を形成するための撥水液。
A siloxane compound represented by the general formula [2-1-A],
A water-repellent liquid for forming a water-repellent film, which contains an organic solvent, water, and an acid, and has a mass ratio of the fluoroalkylsilane compound to the siloxane compound of 1: 2 to 1: 3.
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