CN104364294B - Silane compound containing holo-fluorine polyester and surface conditioning agent - Google Patents
Silane compound containing holo-fluorine polyester and surface conditioning agent Download PDFInfo
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- CN104364294B CN104364294B CN201380030939.6A CN201380030939A CN104364294B CN 104364294 B CN104364294 B CN 104364294B CN 201380030939 A CN201380030939 A CN 201380030939A CN 104364294 B CN104364294 B CN 104364294B
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 109
- -1 Silane compound Chemical class 0.000 title claims abstract description 82
- 239000011737 fluorine Substances 0.000 title claims abstract description 81
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 78
- 229920000728 polyester Polymers 0.000 title claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 title claims description 66
- 230000003750 conditioning Effects 0.000 title claims description 60
- 239000002689 soil Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 62
- 239000000463 material Substances 0.000 claims description 55
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 125000001153 fluoro group Chemical group F* 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 16
- 230000003252 repetitive Effects 0.000 claims description 14
- NBVXSUQYWXRMNV-UHFFFAOYSA-N Fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 13
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 53
- 239000002585 base Substances 0.000 description 51
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 47
- 239000010408 film Substances 0.000 description 38
- 238000000034 method Methods 0.000 description 22
- 239000003921 oil Substances 0.000 description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- 238000007792 addition Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 229920002545 silicone oil Polymers 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000005253 cladding Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010702 perfluoropolyether Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing Effects 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000003068 static Effects 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- DFUYAWQUODQGFF-UHFFFAOYSA-N 1-ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound CCOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F DFUYAWQUODQGFF-UHFFFAOYSA-N 0.000 description 3
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N Perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 3
- 210000002381 Plasma Anatomy 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 210000002268 Wool Anatomy 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 229960004624 perflexane Drugs 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical compound [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N Hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- DLHYHXMSPLUHRA-UHFFFAOYSA-N Perfluoromethylcyclohexane Chemical compound FC1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)C(F)(F)F DLHYHXMSPLUHRA-UHFFFAOYSA-N 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N Tantalum pentoxide Chemical compound O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N Tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atoms Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229940008099 dimethicone Drugs 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000011068 load Methods 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052904 quartz Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BRWBDEIUJSDQGV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-methoxyhexane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BRWBDEIUJSDQGV-UHFFFAOYSA-N 0.000 description 1
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical class COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- NOPJRYAFUXTDLX-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-methoxypropane Chemical compound COC(F)(F)C(F)(F)C(F)(F)F NOPJRYAFUXTDLX-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QEWYKACRFQMRMB-UHFFFAOYSA-N Fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 1
- 241000282574 Gorilla gorilla Species 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N M-Xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L Magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 210000000713 Mesentery Anatomy 0.000 description 1
- 241000972349 Ocoa Species 0.000 description 1
- 229910009973 Ti2O3 Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N Titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N Trifluorotoluene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N [O--].[Zn++].[In+3] Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- YCIVSJFIXXVSRH-UHFFFAOYSA-N amino-methyl-phenylsilicon Chemical compound C[Si](N)C1=CC=CC=C1 YCIVSJFIXXVSRH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical class [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides a kind of new silane compound containing holo-fluorine polyester, and it is represented by any one of following formula (1a), (1b), (2a) and (2b), and number-average molecular weight is 6 × 103～1 × 105, it is possible to formed and there is water-repellancy, group oiliness, soil resistance and there is the layer of high friction durability.In formula, Rf1、Rf2、a、b、c、d、e、f、g、h、i、j、k、l、m、n、X、Y、Z、T、R1And R2Represent respectively and the same meaning described in description.
Description
Technical field
The present invention relates to the silane compound containing holo-fluorine polyester.The invention still further relates to use this containing PFPE
The surface conditioning agent etc. of the silane compound of base.
Background technology
Some fluorine containing silane compound known is when processing for the surface of base material, using the teaching of the invention it is possible to provide excellent water-repellancy, dial
Oiliness, soil resistance etc..(hereinafter also referred to " surface processes the layer obtained by the surface conditioning agent containing fluorine containing silane compound
Layer "), as so-called functional film, it is applied on the various base materials such as such as glass, plastics, fiber, construction material.
As this fluorine containing silane compound, it is known that there is on molecular backbone holo-fluorine polyester, at molecular end or end
End has the silane compound containing holo-fluorine polyester of the group that can hydrolyze being combined with Si atom (with reference to patent documentation
1～2).When the surface conditioning agent comprising this silane compound containing holo-fluorine polyester is applied on base material, with Si atom
In conjunction with the group that can hydrolyze and react between compound between base material and combine, it is possible to form surface and process
Layer.
Citation
Patent documentation 1: International Publication the 97/07155th
Patent documentation 2: Japanese Unexamined Patent Application Publication 2008-534696 publication
Summary of the invention
Invention to solve the technical problem that
In order to base material provide long-term desired by function, surface-treated layer needs high-durability.By comprising containing complete
The layer that the surface conditioning agent of the silane compound of perfluoroalkyl polyether base obtains, even if also be able to play above-mentioned in the case of thin film
Function, so, be suitable for demand light transmission or even the optics of the glasses of the transparency or touch screen etc., particularly at this
In a little purposes, it is desirable to the further raising of friction durability.
But, utilize the layer obtained by the existing surface conditioning agent comprising the silane compound containing holo-fluorine polyester,
Can not say and can fully meet the requirement increasing friction durability stepped up.
It is an object of the invention to provide a kind of new silane compound containing holo-fluorine polyester, it can be formed has
Water-repellancy, dial oiliness, soil resistance and there is the layer of high friction durability.The present invention also aims to provide use and should contain entirely
The silane compound of perfluoroalkyl polyether base and the surface conditioning agent etc. that obtains.
For solving the means of technical problem
Main points according to the present invention, it is provided that a kind of silane compound containing holo-fluorine polyester, it is by following formula
(1a) any one and in (1b) represents, number-average molecular weight is 6 × 103～1 × 105,
(in these formulas, Rf1Expression can replace the alkyl of the carbon number 1～16 having 1 or more fluorine atom,
A, b, c and s are separately the integer of less than more than 0 200, and a, b, c and s sum are at least 1, mark a, b, c
Or the existence order of each repetitive of bracketing of the bracket of s is arbitrary in formula,
D and f is 0 or 1,
E and g is the integer of less than more than 02,
M and l is the integer of less than more than 1 10,
X represents hydrogen atom or halogen atom,
Y represents hydrogen atom or low alkyl group,
Z represents fluorine atom or lower fluoro-alkyl,
T represents the group that hydroxyl maybe can hydrolyze,
R1Represent hydrogen atom or the alkyl of carbon number 1～22,
N is the integer of less than more than 13.)
It addition, in the present invention, when there is multiple same-sign in certain formula, they can select independently of one another.
Another main points according to the present invention, it is provided that a kind of silane compound containing holo-fluorine polyester, it is by following logical
Any one in formula (2a) and (2b) represents, number-average molecular weight is 6 × 103～1 × 105,
(in these formulas, Rf2Expression can replace the alkyl of the carbon number 1～16 having 1 or more fluorine atom,
A, b, c and s are separately the integer of less than more than 0 200, and a, b, c and s sum are at least 1, mark a, b, c
Or the existence order of each repetitive of bracketing of the bracket of s is arbitrary in formula,
D and f is 0 or 1,
H and j is 1 or 2,
I and k is the integer of less than more than 2 20,
Z represents fluorine atom or lower fluoro-alkyl,
T represents the group that hydroxyl maybe can hydrolyze,
R2Represent hydrogen atom or the alkyl of carbon number 1～22,
N is the integer of less than more than 13.)
Another main points according to the present invention, it is provided that a kind of surface conditioning agent, it comprises number-average molecular weight is 6 × 103～1
×105Silane compound containing holo-fluorine polyester shown in above-mentioned formula (1a), (1b), (2a) and (2b) (following, represent
These compounds sometimes referred to simply as " the fluorine containing silane compound of the present invention ") at least one or their mixture.
The surface conditioning agent of such present invention, it is possible to base material gives water-repellancy, to dial oiliness, soil resistance, friction durable
Property, it is possible to it is suitable as soil resistance smears, but is not particularly limited.
Another main points according to the present invention, it is provided that a kind of include base material and on this substrate surface formed layer (surface
Process layer) article, this layer is formed by the above-mentioned silane compound containing holo-fluorine polyester or above-mentioned surface conditioning agent.These article
In layer there is water-repellancy, dial oiliness, soil resistance, and there is high friction durability.
The article obtained by the present invention can be such as optics, but is not particularly limited.Optics is for improving
The demand of friction durability is high, is suitable for utilizing the present invention.Above-mentioned base material can be such as glass or transparent plastic.Wherein, at this
In invention, so-called " transparent " can be to be generally acknowledged to transparent concept, such as, mean that haze value is below 5%.
Invention effect
In accordance with the invention it is possible to provide a kind of new silane compound containing holo-fluorine polyester, the feature of this compound
It is that number-average molecular weight is 6 × 103～1 × 105, thereby, it is possible to formed, there is water-repellancy, group oiliness, soil resistance, and have
The layer of high friction durability.It addition, in accordance with the present invention it is further possible to provide use the table that the fluorine containing silane compound of the present invention obtains
Face inorganic agent and their article of use.
Accompanying drawing explanation
Fig. 1 is to represent that the friction of the surface-treated layer made in embodiments of the invention 1～6 and comparative example 1～3 is durable
The chart of property.
Detailed description of the invention
Below, the article that they obtain to fluorine containing silane compound, surface conditioning agent and the use of the present invention are carried out in detail
Illustrate, but the present invention is not limited to this.
Number-average molecular weight is 6 × 103～1 × 105The silane compound containing holo-fluorine polyester
In a mode of the present invention, the fluorine containing silane compound of the present invention is characterised by: by following formula (1a)
(1b) any one in represents, number-average molecular weight is 6 × 103～1 × 105。
In another mode of the present invention, the fluorine containing silane compound of the present invention is characterised by: by following formula
(2a) any one and in (2b) represents, number-average molecular weight is 6 × 103～1 × 105。
In these formulas, Rf1And Rf2Expression can replace the (the most straight of the carbon number 1～16 of the fluorine atom having more than 1
Chain or branched) alkyl, preferably can replace straight-chain or the side chain of the carbon number 1～3 of the fluorine atom having more than 1
The alkyl of shape.The most above-mentioned alkyl that can replace the fluorine atom having more than 1 be terminal carbon be CF2H-, other institute
Some carbon atoms all replace fluoro-alkyl or the perfluoroalkyl having fluorine, more preferably perfluoroalkyl, are specially-CF3,-CF2CF3
Or-CF2CF2CF3。
In above-mentioned formula, holo-fluorine polyester is-(OC4F8)s-(OC3F6)a-(OC2F4)b-(OCF2)c-shown part.
A, b, c and s represent 4 kinds of number of repeat unit of the PFPE constituting principal polymer backbone respectively, are more than 0 independently of one another
The integer of less than 200, the integer of for example, less than more than 1 200, a, b, c and s sum be at least 1, and preferably 20～100, more excellent
Select 30～50, the most about 40.The existence order of each repetitive that the bracket of mark footmark a, b, c or s brackets exists
Formula is arbitrary.In these repetitives ,-(OC4F8)-can be-(OCF2CF2CF2CF2)-,-(OCF (CF3)
CF2CF2)-,-(OCF2CF(CF3)CF2)-,-(OCF2CF2CF(CF3))-,-(OC (CF3)2CF2)-,-(OCF2C
(CF3)2)-and-(OCF (CF3)CF(CF3))-in wantonly 1, preferably-(OCF2CF2CF2CF2)-.-(OC3F6)-can
To be-(OCF2CF2CF2)-,-(OCF (CF3)CF2)-and-(OCF2CF(CF3))-wantonly 1, preferably-
(OCF2CF2CF2)-.-(OC2F4)-can be-(OCF2CF2)-and-(OCF (CF3))-wantonly 1, preferably-
(OCF2CF2)-.
Such compound containing holo-fluorine polyester can show the water-repellancy of excellence, dial oiliness and soil resistance (example
As prevented the attachment of the dirts such as fingerprint).
In above-mentioned formula, d and f is 0 or 1, e and g is the integer of less than more than 02.
In above-mentioned formula, h and j is 1 or 2, i and k is the integer of less than more than 2 20.
X represents hydrogen atom or halogen atom.Halogen atom is preferably atomic iodine, chlorine atom, fluorine atom, more preferably atomic iodine.
Y represents hydrogen atom or low alkyl group, the alkyl of the preferred carbon number of low alkyl group 1～20.
Z represents fluorine atom or lower fluoro-alkyl.The fluoro-alkyl of lower fluoro-alkyl for example, carbon number 1～3, excellent
Select the perfluoroalkyl of carbon number 1～3, more preferably trifluoromethyl, pentafluoroethyl group, further preferred trifluoromethyl.
Rf1And Rf2Can be the perfluoroalkyl of carbon number 1～3, b=0, c=0, d=1, f=1, preferably Z be that fluorine is former
Son, but it is not limited to this.Now, it is possible to obtain suitable friction durability.It addition, the bracket of more preferably mark footmark a includes
The repetitive got up-(OC3F6)-be-(OCF2CF2CF2)-, a=40.Now, holo-fluorine polyester has straight-chain knot
Structure, compared with the situation with branched structure, it is possible to obtains height friction durability, also has the easy advantage of synthesis.
T、R1And R2It it is the group being combined with Si.N is the integer of less than more than 13.
R1And R2Represent the alkyl of carbon number 1～22, the alkoxyl of carbon number 1～22 or hydroxyl, preferably carbon number
The alkyl of the alkyl of 1～22 or the alkoxyl of carbon number 1～22, more preferably carbon number 1～3 or the alkane of carbon number 1～3
Epoxide.Hydroxyl can be the alkoxyl hydrolysis of carbon number 1～22 and the hydroxyl that generates, but is not particularly limited.
T represents the group that hydroxyl maybe can hydrolyze, as the example of the group that can hydrolyze, can enumerate-OA-,-
OCOA ,-O-N=C (A)2,-N (A)2,-NHA, (in these formulas, A represents substituted or non-substituted carbon number 1～3 to halogen
Alkyl) etc..
M and l is the integer of less than more than 1 10.The integer of m and l preferably less than more than 26.
Above-mentioned formula (1a) and (1b) and formula (2a) and the fluorine containing silane compound of the present invention shown in (2b), counting
When average molecular weight is too low, it is impossible to obtain height friction durability, and when too high, the processing method of base material will be restricted,
So, have 6 × 103～1 × 105Number-average molecular weight (hereinafter also referred to as " mean molecule quantity "), preferably 6 × 103～3
×104, more preferably 7 × 103～3 × 104, further preferred 7 × 103～1 × 104, specifically there is the number-average molecular weight of about 8000.
By having such number-average molecular weight, the fluorine containing silane compound of the present invention can obtain high friction durability, and to base
The process of material becomes easy.
The fluorine containing silane compound of the present invention shown in above-mentioned formula (1a), (1b), (2a) and (2b) can be a kind or 2
Plant above mixture.In the mixture, each compound can exist with 1～99 weight %, but is not limited to this.
The fluorine containing silane compound of the above-mentioned present invention, it is possible to by the most suitable method manufacture.Such as can pass through
Following method manufacture, but it is not limited to this.
About above-mentioned formula (1a) and the fluorine containing silane compound of any one shown present invention of (1b), first, as
Raw material, prepares the compound of any one shown at least one of following formula (1a-ii) and (1b-ii):
(in formula, X ' represents halogen atom, preferred iodine, and other symbol is ibid).Such compound such as can by under
The compound of any one the shown at least one stating formula (1a-i) and (1b-i) is implemented halogenation (such as iodate) and is obtained
Arrive, but be not limited to this.
(in formula, the implication of each symbol is ibid.)
By making compound and the CH of any one shown at least one of this formula (1a-ii) and (1b-ii)2=
CY-(CH2)e-SiX "nR1 3-nWith T-H or CH2=CY-(CH2)e-SiTnR1 3-n(" for halogen atom, other symbol in formula, X
Ibid) reaction, obtains the compound of any one shown at least one of above-mentioned formula (1a) and (1b).
About above-mentioned formula (2a) and the fluorine containing silane compound of any one shown present invention of (2b), first, make work
For following formula (2a-i) and any one shown at least one compound of (2b-i) of raw material, at transition metal, preferred platinum
Or in the presence of rhodium, use HSiX1 nR2 3-n(in formula, X1For halogen atom, preferred chlorine, other symbol is ibid) carry out silicon hydrogenation instead
Should, obtain the compound of any one shown at least one of following formula (2a-ii) and (2b-ii).
By utilizing TH (in formula, T ibid, but does not include hydroxyl) to any one of this formula (2a-ii) and (2b-ii)
The compound dehalogenation of shown at least one, obtains the chemical combination of wantonly 1 shown at least one of above-mentioned formula (2a) and (2b)
Thing.
Above, the fluorine containing silane compound of the present invention is illustrated, but the fluorine containing silane compound of the present invention does not limits
Due to the compound obtained by this example.
As described below, the compound of the present invention can be efficiently used for surface conditioning agent, but is not limited to this, such as, also
Can use as lubricant, solubilizing agent.
Surface conditioning agent
As long as the surface conditioning agent of the present invention comprises the fluorine containing silane compound of the invention described above.That is, comprise above-mentioned
The fluorine containing silane chemical combination of the present invention shown in the fluorine containing silane compound of the present invention shown in formula (1a) and above-mentioned formula (1b)
At least one of thing, it is also possible to comprise both.When both are applied in combination, the compound shown in formula (1a) and formula
(1b) compound shown in such as can exist with mass ratio 10: 1～1: 1, but is not limited to this.
It addition, the surface conditioning agent of the present invention can comprise the fluorine containing silane chemical combination of the present invention shown in above-mentioned formula (2a)
At least one of the fluorine containing silane compound of the present invention shown in thing and above-mentioned formula (2b), it is also possible to comprise both.To
When both are applied in combination, the compound shown in formula (2a) and the compound shown in formula (2b) such as can be with mass ratioes 10: 1
～exist at 1: 1, but it is not limited to this.
Further, in the surface conditioning agent of the present invention, the present invention shown in above-mentioned formula (1a), (1b), (2a) and (2b)
Fluorine containing silane compound can contain in the way of one kind or two or more mixture.Containing sometimes in the way of mixture, respectively
Compound can exist with 1～99 weight % of the whole amount of the fluorine containing silane compound of the present invention, preferably 10～90 weight %
Exist, but be not limited to this.
As long as the fluorine containing silane compound that surface conditioning agent is containing the present invention is as main component or effective ingredient.?
This, so-called " main component " refers to that the composition more than 50 weight % of the content in surface conditioning agent, so-called " effective ingredient " refer to
Remain on the base material needing surface to process and form surface-treated layer, it is possible to making it show some function (water-repellancy, group oil
Property, soil resistance, surface slipperiness, friction durability etc.) composition.
The surface conditioning agent of the present invention contains the fluorine containing silane compound of the present invention, it is possible to is formed and has water-repellancy, group oil
Property, soil resistance and there is high friction durability and the surface-treated layer of surface slipperiness, thus it is possible to effectively serve as soil resistance
Smears.
The composition of the surface conditioning agent (or surface process constituent) of the present invention can be according to desired by surface-treated layer
Function suitably selects.
The surface conditioning agent of the present invention, in addition to the fluorine containing silane compound comprising the present invention, it is also possible to comprise number all
Molecular weight is 1 × 103～5 × 103The silicon containing holo-fluorine polyester shown in above-mentioned formula (1a), (1b), (2a) and/or (2b)
Hydride compounds.The fluorine containing silane compound of fluorine containing silane compound and low-molecular-weight by being applied in combination high molecular, than list
The situation solely using the fluorine containing silane compound of high molecular is compared, it is possible to obtain more excellent friction durability.By them
When being applied in combination, the fluorine containing silane compound of the present invention and number-average molecular weight are 1 × 103～5 × 103Fluorine containing silane compound
Can exist with mass ratio 10: 1～1: 10, preferably 5: 1～1: 5, more preferably 1: 1～1: 2, but be not limited to this.The equal molecule of number
Amount is 1 × 103～5 × 103Fluorine containing silane compound, preferably have 2 × 103～5 × 103Number-average molecular weight, more preferably have
There is the number-average molecular weight of about 4000.
It addition, the surface conditioning agent of the present invention, in addition to the fluorine containing silane compound comprising the present invention, it is also possible to comprise
It will be appreciated that be that the Fluoropolyether compound containing fluorocarbon oil, preferred per-fluoro polyether compound are (below, for the fluorine silicon with the present invention
Hydride compounds is distinguished, and is referred to as " containing fluorocarbon oil ").Not there is the position (such as silicyl) reactive with base material containing fluorocarbon oil.Fluorine-containing
Oil is favorably improved the surface slipperiness of surface-treated layer.
In surface conditioning agent, relative to 100 mass parts (two or more time be their total, lower with) containing perfluor
The silane compound of polyether-based, the content containing fluorocarbon oil can be such as 0～300 mass parts, preferably 50～200 mass parts.
As such containing fluorocarbon oil, the compound (per-fluoro polyether compound) shown in following formula (3) can be enumerated.
R21-(OC4F8)s′-(OC3F6)a′-(OC2F4)b′-(OCF2)c′-R22…(3)
In formula, R21Expression can replace the alkyl of the carbon number 1～16 of the fluorine atom having more than 1, preferably can take
, there is the alkyl of the carbon number 1～3 of the fluorine atom of more than 1 in generation.The most above-mentioned alkane that can replace the fluorine atom having more than 1
Base be terminal carbon be CF2H-, other all carbon atoms all replace fluoro-alkyl or the perfluoroalkyl having fluorine, more preferably
Perfluoroalkyl.
R22Represent hydrogen atom, fluorine atom or the alkane of carbon number 1～16 of the fluorine atom having more than 1 can be replaced
Base, preferably can replace the alkyl of the carbon number 1～3 of the fluorine atom having more than 1.The most above-mentioned can replace have 1 with
On the alkyl of fluorine atom be terminal carbon be CF2H-, other all carbon atoms all replace the fluoro-alkyl of fluorine or complete
Fluoroalkyl, more preferably perfluoroalkyl.
A ', b ', c ' and s ' represent 4 kinds of number of repeat unit of the PFPE of the main framing constituting polymer respectively, each other
Independently be the integer of less than more than 0 300, such as, the integer of less than more than 1 300, a ', b ', c ' and s ' sum are at least 1, excellent
Select 1～100.The existence order of each repetitive that the bracket of mark footmark a ', b ', c ' or s ' brackets is any in formula
's.In these repetitives ,-(OC4F8)-can be-(OCF2CF2CF2CF2)-,-(OCF (CF3)CF2CF2)-,-
(OCF2CF(CF3)CF2)-,-(OCF2CF2CF(CF3))-,-(OC (CF3)2CF2)-,-(OCF2C(CF3)2)-,-
(OCF(CF3)CF(CF3))-,-(OCF (C2F5)CF2)-and-(OCF2CF(C2F5))-wantonly 1, preferably-
(OCF2CF2CF2CF2)-.-(OC3F6)-can be-(OCF2CF2CF2)-,-(OCF (CF3)CF2)-and-(OCF2CF
(CF3))-wantonly 1, preferably-(OCF2CF2CF2)-.-(OC2F4)-can be-(OCF2CF2)-and-(OCF
(CF3))-wantonly 1, preferably-(OCF2CF2)-.
As the example of the per-fluoro polyether compound shown in above-mentioned formula (3), following formula (3a) and (3b) can be enumerated
Wantonly 1 shown compound (can be one kind or two or more mixture).
R21-(OCF2CF2CF2)a″-R22……(3a)
R21-(OCF2CF2CF2CF2)s″-(OCF2CF2CF2)a″-(OCF2CF2)b″-(OCF2)c″-R22……(3b)
In these formulas, R21And R22Ibid；In formula (3a), a " is the integer of less than more than 1 100；In formula (3b), b " and c "
Being separately the integer of less than more than 1 300, a " and s " is separately the integer of less than more than 1 30.Mark footmark
The existence order of each repetitive that the bracket of a ", b ", c " and s " brackets is arbitrary in formula.
Compound shown in formula (3a) and the compound shown in formula (3b) can individually use, it is also possible to combination
Use.When these compounds are applied in combination, preferably with mass ratio 1: 1～1: 30 use the compound shown in formula (3a) and
Compound shown in formula (3b).According to such mass ratio, it is possible to the balance obtaining surface slipperiness and friction durability is excellent
Different surface conditioning agent.
It addition, from the viewpoint of other, can be general formula R f containing fluorocarbon oil1-F (in formula, Rf1Change shown in as mentioned above)
Compound.General formula R f1Compound shown in-F and wantonly 1 shown compound of above-mentioned formula (1a), (1b), (2a) and (2b)
Affinity high, thus preferably.
1000～30000, more preferably 3000～the mean molecule quantity of 30000 can be had containing fluorocarbon oil.Thereby, it is possible to obtain
High surface slipperiness.
It addition, the surface conditioning agent of the present invention is in addition to the fluorochemical comprising the present invention, it is also possible to comprising can
It is interpreted as the organo-silicon compound (hereinafter referred to as " silicone oil ") of organic silicone oil.The surface that silicone oil is favorably improved surface-treated layer is sliding
Dynamic property.
In surface conditioning agent, containing the silane compound of holo-fluorine polyester relative to 100 mass parts, the content of silicone oil is such as
Can be 0～300 mass parts, preferably 50～200 mass parts.
As such silicone oil, it is, for example possible to use siliconoxygen bond straight-chain below 2000 or ring-type silicone oil.Straight chain
The silicone oil of shape can be so-called straight silicone oil and modified silicon oil.As straight silicone oil, dimethicone, aminomethyl phenyl silicon can be enumerated
Oil, Methyl Hydrogen Polysiloxane Fluid.As modified silicon oil, can enumerate and utilize alkyl, aralkyl, polyethers, high-grade aliphatic ester, fluoroalkane
Base, amino, epoxy radicals, carboxyl, alcohol etc. are by modified silicon oil that is the most silicon oil modified and that obtain.Cyclic silicone oils such as can be enumerated ring-type
Dimethicone oils etc..
Article
Below, the article using such surface conditioning agent to obtain are illustrated.The article of the present invention include base material and
On the surface of this base material, fluorine containing silane compound or surface conditioning agent by the present invention (below, represent them and are referred to as " surfaces
Inorganic agent ") layer (surface-treated layer) that formed.These article such as can be fabricated as described below.
First, base material is prepared.The base material that can use in the present invention, such as can be by glass, resin (naturally occurring or synthetic tree
Fat, for example, it may be general plastic material, can be tabular, film, other form), metal (can be aluminum, copper, ferrum etc.
The complex of metallic monomer or alloy etc.), pottery, quasiconductor (silicon, germanium etc.), fiber (fabric, non-woven fabrics etc.), fur, leather,
The material composition that timber, ware, stone material etc. are the most suitable.
Such as, when being optics needing the article manufactured, the material on the surface constituting base material can be optics
With material, such as, can be glass or transparent plastic etc..It addition, when the article that needs manufacture are opticses, can be at base
The upper arbitrary layer (or film) that formed in the surface (outermost layer) of material, such as, forms hard conating or anti-reflection layer etc..Anti-reflection layer is permissible
Use any number of of monolayer anti-reflection layer and multilamellar anti-reflection layer.Example as the inorganic matter that can use in anti-reflection layer
Son, can enumerate SiO2、SiO、ZrO2、TiO2、TiO、Ti2O3、Ti2O5、Al2O3、Ta2O5、CeO2、MgO、Y2O3、SnO2、MgF2、
WO3Deng.These inorganic matters can be used alone or their two or more combination (such as with the form of mixture) used.?
In the case of multilamellar anti-reflection layer, preferably its outermost layer uses SiO2And/or SiO.Needing the article manufactured to be, touch screen is used
Optical glass part time, the part on the surface of base material (glass) can have a transparency electrode, such as, has use oxidation
The thin film of indium stannum (ITO) or indium zinc oxide etc..It addition, according to its concrete pattern etc., base material can have insulating barrier, bonding
Layer, protective layer, escutcheon layer (I-CON), sprayed film layer, hard coat film, light polarizing film, phase retardation film and LCD MODULE etc..
The shape of base material is not particularly limited.In addition, it is necessary to the region, surface forming the base material of surface-treated layer can be
Substrate surface at least some of, it is possible to the purposes of the article manufactured as required and concrete pattern etc. suitably determine.
As such base material, can at least its surface portion be made up of the material originally with hydroxyl.As such
Material, can enumerate glass, it is also possible to is set forth in surface and is formed with metal (the low-pricedest gold of natural oxide film or heat oxide film
Belong to), pottery, quasiconductor etc..Or, as resin etc., although there is hydroxyl but insufficient situation or originally do not have
In the case of hydroxyl, by base material is implemented arbitrary pre-treatment, it is possible to import hydroxyl on the surface of base material or make hydroxyl increase.
As the example of such pre-treatment, Cement Composite Treated by Plasma (such as sided corona treatment) or ion beam irradiation can be enumerated.Plasma
Body processes and can import hydroxyl at substrate surface or make hydroxyl increase, and substrate surface can be made to clean (removing foreign body
Deng), thus be suitable for utilizing.It addition, as another example of such pre-treatment, can enumerate by LB method (Langmuir-
Blodgett method) or chemiadsorption etc., with the form formation of monomolecular film, there is unsaturated carbon carbon bond at substrate surface in advance
Interfacial Adsorption agent, afterwards, under the atmosphere comprising oxygen or nitrogen etc., make the method that unsaturated bond ftractures.
It addition, as such base material, it is also possible to it is that at least its surface portion is by organo-silicon compound or containing alkoxyl
The base material that the material of silane is constituted, wherein, above-mentioned organo-silicon compound have other the reactive group of more than 1, such as
Si-H base.
Then, form the film of above-mentioned surface conditioning agent on the surface of such base material, locate after as required this film being carried out
Reason, thus, is formed surface-treated layer by surface conditioning agent.
The formation of the film of surface conditioning agent, can make it cover this by substrate surface is applied above-mentioned surface conditioning agent
Surface is implemented.Covering method is not particularly limited.It is, for example possible to use moistening cladding process and dry cladding process.
As the example of moistening cladding process, dip-coating, spin coating, flow coat, spraying, roller coat, intaglio plate coating can be enumerated with similar
Method.
As the example of dry cladding process, vacuum evaporation, sputtering, CVD and similar method can be enumerated.Steam as vacuum
The object lesson of plating method, can enumerate resistance heating, electron beam, high-frequency heating, ion beam and similar method.As CVD side
The object lesson of method, can enumerate plasma CVD, optics CVD, hot CVD and similar method.
Can also carry out utilizing the covering of atmospheric plasma method.
When using moistening cladding process, surface conditioning agent can be applied to substrate surface with after solvent dilution.From surface
From the viewpoint of the stability of inorganic agent and the volatility of solvent, following solvent it is preferably used: the perfluor fat of carbon number 5～12
Fat race hydrocarbon (such as, perflexane, perfluoromethylcyclohexane (PFMCH) and perfluor-1,3-dimethyl cyclohexane)；Polyfluoro aromatic hydrocarbon (example
As, double (trifluoromethyl) benzene)；Polyfluoro aliphatic hydrocarbon；Hydrofluoroether (HFE) (such as, perfluoro propyl methyl ether (C3F7OCH3), perfluor
Butyl methyl ether (C4F9OCH3), perfluorobutyl ethyl ether (C4H9OC2H5), perfluoro hexyl methyl ether (C2F5CF(OCH3)C3F7) etc.
Alkyl perfluoroalkyl ethers (perfluoroalkyl and alkyl can be straight-chain or branched)) etc..These solvents can be used alone
Or use with the form of mixture of more than two kinds.Wherein, preferably hydrofluoroether, particularly preferred perfluorobutyl methyl ethers (C4F9OCH3)
And/or perfluorobutyl ethyl ether (C4H9OC2H5)。
Preferably, preferred surface inorganic agent and the catalyst for hydrolysis and dehydrating condensation coexist ground in fact in film in the formation of film
Execute.Easily, when utilizing moistening cladding process, can after surface conditioning agent being diluted with solvent, base will be applied to
Before material surface, the diluent of surface conditioning agent adds catalyst.When utilizing dry cladding process, can be directly to interpolation
The surface conditioning agent of catalyst carries out vacuum evaporation process, or can use and to be impregnated with in the metal porous body of ferrum or copper etc.
The particulate matter having the surface conditioning agent that with the addition of catalyst carries out vacuum evaporation process.
Catalyst can use the most suitable acid or alkali.As acid catalyst, it is, for example possible to use acetic acid, formic acid, three
Fluoroethanoic acid etc..It addition, as base catalyst, it is, for example possible to use ammonia, organic amine etc..
Then, as required film is carried out post processing.This post processing is not particularly limited, for example, it is possible to implement step by step
Moisture supply and dry heat, can operate enforcement in detail as follows.
After the film forming surface conditioning agent as mentioned above at substrate surface, supply to this film (hereinafter also referred to " precursor film ")
To moisture.The supply method of moisture is not particularly limited, it is, for example possible to use utilize precursor film (and base material) and ambient atmosphere
Temperature difference and the condensation that causes or the method blowing attached water steam (steam) etc..
It is believed that when moisture is fed on precursor film, water will with in surface conditioning agent containing holo-fluorine polyester
Silane compound Si on combine substituted-amino (and in the presence of, at the silane compound containing holo-fluorine polyester
The group that can hydrolyze of the upper combination of Si) have an effect, it is possible to make this compound promptly hydrolyze.
The supply of moisture such as can be implemented under the atmosphere of 0～500 DEG C, preferably more than 100 DEG C less than 300 DEG C.At this
Within the temperature range of sample, by supply moisture, it is possible to make hydrolysis carry out.Pressure now is not particularly limited, the most permissible
For normal pressure.
Then, on the surface of this base material, higher than under the dry atmosphere of 60 DEG C, this precursor film is heated.It is dried and adds
By the use of thermal means is not particularly limited, and can be placed on by precursor film higher than 60 DEG C, is preferably above the temperature of 100 DEG C together with base material,
Such as less than 500 DEG C, the temperature of preferably less than 300 DEG C, and under the atmosphere of unsaturated water vapor pressure.Pressure now does not has spy
Do not limit, can be normal pressure easily.
Under such atmosphere, the present invention fluorine containing silane compound (and in the presence of, mean molecule quantity is 1 ×
103～5 × 103The silane compound containing holo-fluorine polyester) between, on the Si after hydrolysis combine group between promptly
Dehydrating condensation.It addition, between such compound and base material, the group that the Si after the hydrolysis of this compound combines and base
React rapidly between the reactive group that material surface exists, the dehydrating condensation when the reactive group that substrate surface exists is hydroxyl
(wherein, between the compound so combined, in the presence of, be mixed containing fluorocarbon oil and/or silicone oil).As a result, in the present invention
Fluorine containing silane compound (and in the presence of, mean molecule quantity is 1 × 103～5 × 103The silane containing holo-fluorine polyester
Compound) between bonding, and, between this compound and base material bonding (and in the presence of, containing fluorocarbon oil and/or silicone oil by
In with the fluorine containing silane compound of the present invention (and in the presence of, mean molecule quantity is 1 × 103～5 × 103Containing perfluor gather
The silane compound of ether) affinity and be kept or catch).
Above-mentioned moisture supply and dry heat can also be implemented continuously by using overheated steam.
Overheated steam is gas saturated steam being heated to temperature more higher than boiling point and obtaining, and surpasses at ambient pressure
Cross 100 DEG C, generally below 500 DEG C, the temperature of such as less than 300 DEG C, formed not by being heated to above the temperature of boiling point
Saturated water vapor pressure.The base material being once formed with precursor film is exposed in overheated steam, firstly, since overheated steam with relatively
Temperature difference between the precursor film of low temperature, will produce condensation, thus, to precursor film for giving moisture on precursor film surface.No
For a long time, along with the temperature difference between overheated steam and precursor film reduces, the moisture on precursor film surface produces utilizing overheated steam
Gasifying in raw dry atmosphere, the water quantities on precursor film surface is gradually reduced.The process that water quantities on precursor film surface declines
In, i.e. during precursor film is in dry atmosphere, contacted with overheated steam by the precursor film of substrate surface, added
Heat is to the temperature (temperature higher than 100 DEG C at ambient pressure) of this overheated steam.Therefore, if using overheated steam, as long as
The base material that will be formed with precursor film is exposed in overheated steam, it becomes possible to implement moisture supply and dry heat continuously.
Post processing can be implemented as mentioned above.Such post processing, can in order to improve further friction durability and reality
Execute, it should be noted that manufacture the present invention article time it is not necessary to.For example, it is also possible to surface conditioning agent is being applied to
After substrate surface, stand with keeping intact.
As it has been described above, form the surface-treated layer being derived from surface conditioning agent film at substrate surface, manufacture the goods of the present invention.
Thus obtained surface-treated layer can have water-repellancy, dial oiliness, soil resistance (such as preventing the attachment of the dirts such as fingerprint), table
Face sliding (or lubricity, such as, the property wiped of the dirts such as fingerprint and the excellent sense of touch to finger), friction durability etc., suitable
Cooperation utilizes for functional film.
There are the article of thus obtained surface-treated layer, be not particularly limited, can be optics.Optics
Example can be listed below: the lens of glasses etc.；The front surface protection plate of the display of PDP, LCD etc., antireflection plate, polaroid,
Antiglare shield；The touch screen of the machine of mobile phone, portable data assistance etc.；Blue light (Blu-ray (registered trade mark)) CD, DVD light
The cd side of the CD such as dish, CD-R, MO；Optical fiber etc..
The thickness of surface-treated layer is not particularly limited.In the case of optics, the thickness of surface-treated layer be 1～
The scope of 30nm, preferably 1～the scope of 15nm, go out from the viewpoint of optical property, surface slipperiness, friction durability and soil resistance
It is preferred for sending out.
Above, the article obtained the surface conditioning agent of the use present invention have been described in detail.But the table of the present invention
The manufacture method etc. of the purposes of face inorganic agent, using method and article is not limited to above-mentioned illustration.
Embodiment
The most specifically to fluorine containing silane compound, surface conditioning agent and the use of the present invention, they obtain to utilize embodiment
To article illustrate, but the present invention is not limited to these embodiments.Wherein, in the present embodiment, the 4 of PFPE is constituted
Plant repetitive (CF2O)、(CF2CF2O)、(CF2CF2CF2And (CF O)2CF2CF2CF2O) existence order is arbitrary.
Synthesis example 1
45g is added with average composition in being mounted with the 4 of 200mL of reflux condenser, thermometer and agitator mouthfuls of flasks
CF3CF2CF2O(CF2CF2CF2O)43CF2CF2Perfluoropolyether-modified iodine body that-I represents, 45g hexafluoro meta-xylene, 3.85g second
Thiazolinyl trichlorosilane, under nitrogen flowing to be stirred at room temperature 30 minutes.Then, add 0.68g di-tert-butyl peroxide, be warmed up to
120 DEG C, stir 12 hours with this temperature.Afterwards, volatile ingredient is under reduced pressure distilled off, thus obtains 46g end and have
The following silane compound containing holo-fluorine polyester of iodine.
(integer that in formula, n is 43, m is 1～6)
Synthesis example 2
46g is added in synthesis example 1 in the 4 of 200mL of reflux condenser, thermometer and agitator mouthfuls of flasks are installed
The end of synthesis has the silane compound containing holo-fluorine polyester of iodine, 45g perflexane, 1.8g zinc powder, under nitrogen flowing
Stir 30 minutes with 5 DEG C.Then, after 5～10 DEG C of dropping 20g methanol, heat up, stir 7 hours with 45 DEG C.Afterwards, 25g is added
Perflexane carries out separatory standing, takes out lower floor, afterwards, volatile ingredient is under reduced pressure distilled off, obtains following the containing of 40g
There is the silane compound (A) of holo-fluorine polyester.
(the integer that in formula, n is 43, m is 1～6.)
(embodiment 1)
The preparation of surface conditioning agent
By the compound (molecular weight about 8000) shown in 20 weight portion following formula (A) and 80 weight portion hydrofluoroether (3M companies
Production, Novec HFE7200 (perfluorobutyl ethyl ether)) mixing, prepare surface conditioning agent A.
(the integer that in formula, n is 43, m is 1～6.)
Base material
As base material, use chemically reinforced glass (Corning Incorporated's production, " Gorilla " glass, thickness 0.55mm, plane
Size 55mm × 100mm).Do not carry out the pre-treatment to base material.
The formation of surface-treated layer
Using surface conditioning agent A, on every 1 above-mentioned chemically reinforced glass, vacuum evaporation 2mg surface conditioning agent (processes bar
Part is pressure: 3.0 × 10-3Pa), 20 DEG C, stand 24 hours under the atmosphere of humidity 65%, form curing overlay film.Thus, exist
Substrate surface forms surface-treated layer.
(embodiment 2)
By the compound (molecular weight about 8000) shown in 20 weight portion following formula (B) and 80 weight portion hydrofluoroether (3M companies
Production, Novec HFE7200) mixing, preparation surface conditioning agent B uses, and in addition, operates similarly to Example 1, at base material
Surface forms surface-treated layer.
(CH3O)3-Si-CH2CH2CH2-O-CH2-CF2-*
*-O-(CF2-CF2-O-)p-(CF2-O-)q-CF2-CH2-O-CH2CH2CH2-Si-(OCH3)3 ...(B)
(in formula, p is 40, q is 40.)
(embodiment 3)
By the compound (molecular weight about 8000) shown in 20 weight portion following formula (C) and 80 weight portion hydrofluoroether (3M companies
Production, Novec HFE7200) mixing, preparation surface conditioning agent C uses, and in addition, operates similarly to Example 1, at base material
Surface forms surface-treated layer.
CF3-CF2-CF2-O-(CF2-CF2-CF2-O-)n-CF2-CF2-CH2-O-CH2CH2CH2-Si-(OCH3)3...(C)
(in formula, n is 45.)
(embodiment 4)
By the compound (molecular weight about 8000) shown in the formula (A) in the embodiment 1 of 6.6 weight portions, 13.4 weight portions together
Sample is represented by formula (A) but compound (molecular weight about 4000) that n is 20 and 80 weight portion hydrofluoroether (production of 3M company, Novec
HFE7200) mixing, preparation surface conditioning agent D uses, and in addition, operates similarly to Example 1, forms table at substrate surface
Face processes layer.
(embodiment 5)
Make per-fluoro polyether compound (E) (the Solvay company that compound (A) and following mean molecule quantity are about 25000
Production, FOMBLIN (numbering) M60) it is dissolved in hydrofluoroether (production of 3M company, Novec HFE7200) with the ratio of mass ratio 2: 1
In so that concentration reaches 20wt% (compound (A) and the total of compound (E)), prepares surface conditioning agent, in addition, with
Embodiment 1 operates equally, forms surface-treated layer.
Per-fluoro polyether compound (E)
CF3O(CF2CF2O)139(CF2O)122(CF2CF2CF2O)4(CF2CF2CF2CF2O)4CF3…(E)
(embodiment 6)
Compound (A) and above-mentioned mean molecule quantity is made to be about the per-fluoro polyether compound (E) of 25000 with mass ratio 1: 1
Ratio be dissolved in hydrofluoroether (3M company produce, Novec HFE7200) so that concentration reach 20wt% (compound (A) and
The total of compound (E)), prepare surface conditioning agent, in addition, operate similarly to Example 1, form surface-treated layer.
(comparative example 1)
The compound replacing the molecular weight used in embodiment 1 to be about 8000, use represented by above-mentioned formula (A) equally but point
Son amount is about the compound (integer that in formula, n is 20, m is 1～6) of 4000, in addition, operates similarly to Example 1,
Substrate surface forms surface-treated layer.
(comparative example 2)
The compound replacing the molecular weight used in embodiment 2 to be about 8000, use represented by above-mentioned formula (B) equally but point
Son amount is about the compound (in formula, p is 20, q is 20) of 4000, in addition, operates similarly to Example 2, at substrate surface
Form surface-treated layer.
(comparative example 3)
The compound replacing the molecular weight used in embodiment 3 to be about 8000, use represented by above-mentioned formula (C) equally but point
Son amount is about the compound (in formula, n is 22) of 4000, in addition, operates similarly to Example 3, forms table at substrate surface
Face processes layer.
(evaluation)
For the surface-treated layer formed at substrate surface in above embodiment and comparative example, the static state measuring water connects
Feeler.The static contact angle of water uses contact angle determination device (consonance interface science society produces) to implement with 1 μ L.
First, as initial evaluation, after forming surface-treated layer, when film surface is not in contact with any material,
Measure the static contact angle (Rubbing number 0 time) of water.
Hereafter, as friction durability evaluation, implement steel wool friction durability evaluation.Specifically, will be formed with table
Face processes the base material horizontal arrangement of layer, makes steel wool (model #0000, size 5mm × 10mm × 10mm) and fluorine containing silane mesentery
The upper surface exposed, the loading of the most additional 1000gf, hereafter, make when being applied with loading steel wool with
The speed of 140mm/ second moves back and forth.Every reciprocal time measures static contact angle (the spending) (mensuration at contact angle of water for 1000 times
The value moment less than 100 degree stops evaluating.)
Result (in table, symbol "-" represents undetermined) is represented in table 1 and Fig. 1.
By table 1 and Fig. 1 it has been confirmed that be about the embodiment 1～3 of the fluorine containing silane compound of 8000 at use molecular weight
In, compared with the comparative example 1～3 of the fluorine containing silane compound using molecular weight about 4000, friction durability significantly improves.Separately
Outward, by embodiment 4 it has been confirmed that be mixed with molecular weight be about 8000 fluorine containing silane compound and molecular weight be about 4000 contain
The embodiment 4 of fluorosilane compounds, friction durability significantly improves.Further, by the result of embodiment 5～6 it has been confirmed that mix
Molecular weight is about the fluorine containing silane compound of 8000 and the embodiment 5～6 containing fluorocarbon oil of molecular weight 25000, and rub durability
Significantly improve.
Industrial applicability
The present invention is suitable on various base material, the formation surface, surface of the optics particularly requiring permeability
Process layer.
Claims (13)
1. the silane compound containing holo-fluorine polyester, it is characterised in that:
Being represented by any one in following formula (1a) and (1b), number-average molecular weight is 6 × 103～1 × 104,
In these formulas, Rf1Expression can replace the alkyl of the carbon number 1～16 having 1 or more fluorine atom,
A, b, c and s are separately the integer of less than more than 0 200, and a, b, c and s sum are at least 1, mark a, b, c or s's
The existence order of each repetitive that bracket brackets is arbitrary in formula,
D and f is 0 or 1,
E and g is the integer of less than more than 02,
M and l is the integer of less than more than 1 10,
X represents hydrogen atom or halogen atom,
Y represents hydrogen atom or the alkyl of carbon number 1～20,
Z represents fluorine atom or the fluoro-alkyl of carbon number 1～3,
T represents the group that hydroxyl maybe can hydrolyze,
R1Represent hydrogen atom or the alkyl of carbon number 1～22,
N is the integer of less than more than 13.
2. the silane compound containing holo-fluorine polyester, it is characterised in that:
Being represented by any one in following formula (2a) and (2b), number-average molecular weight is 6 × 103～1 × 105,
In these formulas, Rf2Expression can replace the alkyl of the carbon number 1～16 having 1 or more fluorine atom,
A, b, c and s are separately the integer of less than more than 0 200, and a, b, c and s sum are at least 1, mark a, b, c or s's
The existence order of each repetitive that bracket brackets is arbitrary in formula,
D and f is 0 or 1,
H and j is 1 or 2,
I and k is the integer of less than more than 2 20,
Z represents fluorine atom or the fluoro-alkyl of carbon number 1～3,
T represents the group that hydroxyl maybe can hydrolyze,
R2Represent hydrogen atom or the alkyl of carbon number 1～22,
N is the integer of less than more than 13.
3. the silane compound containing holo-fluorine polyester as claimed in claim 2, it is characterised in that:
Number-average molecular weight is 6 × 103～3 × 104。
4. the mixture of more than two kinds of the silane compound containing holo-fluorine polyester described in a claim 1 or 2.
5. a surface conditioning agent, it is characterised in that:
Comprise the silane compound containing holo-fluorine polyester described in claim 1 or 2.
6. surface conditioning agent as claimed in claim 5, it is characterised in that:
Also comprise any one in following formula (1a), (1b), (2a) and (2b) shown, number-average molecular weight be 1 × 103～5 ×
103The silane compound containing holo-fluorine polyester,
Rf1And Rf2Expression can replace the alkyl of the carbon number 1～16 having 1 or more fluorine atom,
A, b, c and s are separately the integer of less than more than 0 200, and a, b, c and s sum are at least 1, mark a, b, c or s's
The existence order of each repetitive that bracket brackets is arbitrary in formula,
D and f is 0 or 1,
E and g is the integer of less than more than 02,
H and j is 1 or 2,
I and k is the integer of less than more than 2 20,
M and l is the integer of less than more than 1 10,
X represents hydrogen atom or halogen atom,
Y represents hydrogen atom or the alkyl of carbon number 1～20,
Z represents fluorine atom or the fluoro-alkyl of carbon number 1～3,
T represents the group that hydroxyl maybe can hydrolyze,
R1And R2Represent hydrogen atom or the alkyl of carbon number 1～22,
N is the integer of less than more than 13.
7. surface conditioning agent as claimed in claim 5, it is characterised in that:
Also comprise containing fluorocarbon oil.
8. surface conditioning agent as claimed in claim 7, it is characterised in that:
It is the compound shown in following formula (3) containing fluorocarbon oil,
R21-(OC4F8)s′-(OC3F6)a′-(OC2F4)b′-(OCF2)c′-R22 …(3)
In formula, R21Expression can replace the alkyl of the carbon number 1～16 having 1 or more fluorine atom；
R22Represent hydrogen atom, fluorine atom or the alkyl of the carbon number 1～16 having 1 or more fluorine atom can be replaced；
A ', b ', c ' and s ' are separately the integer of less than more than 0 300, and a ', b ', c ' and s ' sum are at least 1, mark angle
The existence order of each repetitive that the bracket of mark a ', b ', c ' or s ' brackets is arbitrary in formula.
9. surface conditioning agent as claimed in claim 7, it is characterised in that:
It is the compound shown in following formula (3b) containing fluorocarbon oil,
R21-(OCF2CF2CF2CF2)s″-(OCF2CF2CF2)a″-(OCF2CF2)b″-(OCF2)c″-R22 …(3b)
In formula, R21Expression can replace the alkyl of the carbon number 1～16 having 1 or more fluorine atom；
R22Represent hydrogen atom, fluorine atom or the alkyl of the carbon number 1～16 having 1 or more fluorine atom can be replaced；
B " and c " is separately the integer of less than more than 1 300,
A " and s " is separately the integer of less than more than 1 30,
The existence order of each repetitive that mark footmark a ", b ", the bracket of c " or s " bracket is arbitrary in formula.
10. the surface conditioning agent as according to any one of claim 5～9, it is characterised in that:
Use as soil resistance smears.
11. 1 kinds of article, it includes base material and by containing entirely according to any one of claims 1 to 3 on this substrate surface
The layer that surface conditioning agent according to any one of the silane compound of perfluoroalkyl polyether base or claim 5～9 is formed.
12. article as claimed in claim 11, it is characterised in that:
Described article are opticses.
13. article as described in claim 11 or 12, it is characterised in that:
Described base material is glass or transparent plastic.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-133683 | 2012-06-13 | ||
| JP2012133683 | 2012-06-13 | ||
| PCT/JP2013/066182 WO2013187432A1 (en) | 2012-06-13 | 2013-06-12 | Silane compound containing perfluoropolyether group and surface-treating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104364294A CN104364294A (en) | 2015-02-18 |
| CN104364294B true CN104364294B (en) | 2016-11-30 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139950A (en) * | 1993-12-29 | 1997-01-08 | 大金工业株式会社 | Fluorinated oil/water emulsion and surface treatment composition |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139950A (en) * | 1993-12-29 | 1997-01-08 | 大金工业株式会社 | Fluorinated oil/water emulsion and surface treatment composition |
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