CN112533932A - Organosilane compound having lipophilic group, surface treatment agent, and article - Google Patents
Organosilane compound having lipophilic group, surface treatment agent, and article Download PDFInfo
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- CN112533932A CN112533932A CN201980050960.XA CN201980050960A CN112533932A CN 112533932 A CN112533932 A CN 112533932A CN 201980050960 A CN201980050960 A CN 201980050960A CN 112533932 A CN112533932 A CN 112533932A
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- -1 Organosilane compound Chemical class 0.000 title claims abstract description 114
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 83
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 210000002374 sebum Anatomy 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 21
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 238000005299 abrasion Methods 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 122
- 239000002904 solvent Substances 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 129
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 111
- 238000006243 chemical reaction Methods 0.000 description 41
- 229910000077 silane Inorganic materials 0.000 description 34
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 29
- 238000005160 1H NMR spectroscopy Methods 0.000 description 25
- 150000001336 alkenes Chemical group 0.000 description 23
- 239000002253 acid Substances 0.000 description 22
- 229910018540 Si C Inorganic materials 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 21
- 239000007788 liquid Substances 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 229910010271 silicon carbide Inorganic materials 0.000 description 21
- 239000010410 layer Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 125000003342 alkenyl group Chemical group 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 150000004756 silanes Chemical class 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 12
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 150000003961 organosilicon compounds Chemical class 0.000 description 7
- 239000004210 ether based solvent Substances 0.000 description 6
- 238000006459 hydrosilylation reaction Methods 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 150000001282 organosilanes Chemical class 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 125000005647 linker group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- CYSFUFRXDOAOMP-UHFFFAOYSA-M magnesium;prop-1-ene;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C=C CYSFUFRXDOAOMP-UHFFFAOYSA-M 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000005400 gorilla glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004344 phenylpropyl group Chemical group 0.000 description 3
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 2
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000005646 oximino group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- QKAGYSDHEJITFV-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane Chemical compound FC(F)(F)C(F)(F)C(F)(OC)C(F)(C(F)(F)F)C(F)(F)F QKAGYSDHEJITFV-UHFFFAOYSA-N 0.000 description 1
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FXNFFCMITPHEIT-UHFFFAOYSA-N Ethyl 10-undecenoate Chemical compound CCOC(=O)CCCCCCCCC=C FXNFFCMITPHEIT-UHFFFAOYSA-N 0.000 description 1
- PTVSRINJXWDIKP-UHFFFAOYSA-N Ethyl 4-pentenoate Chemical compound CCOC(=O)CCC=C PTVSRINJXWDIKP-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000005640 Methyl decanoate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000005641 Methyl octanoate Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005074 adamantylmethyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZXDVQYBUEVYUCG-UHFFFAOYSA-N dibutyltin(2+);methanolate Chemical compound CCCC[Sn](OC)(OC)CCCC ZXDVQYBUEVYUCG-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002634 lipophilic molecules Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- PKLGTKSKHJFCIX-UHFFFAOYSA-N octyl undec-10-enoate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC=C PKLGTKSKHJFCIX-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- NGASWKRTXGWPNN-UHFFFAOYSA-N tert-butyl but-3-enoate Chemical compound CC(C)(C)OC(=O)CC=C NGASWKRTXGWPNN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- IBOKZQNMFSHYNQ-UHFFFAOYSA-N tribromosilane Chemical compound Br[SiH](Br)Br IBOKZQNMFSHYNQ-UHFFFAOYSA-N 0.000 description 1
- UCSBCWBHZLSFGC-UHFFFAOYSA-N tributoxysilane Chemical compound CCCCO[SiH](OCCCC)OCCCC UCSBCWBHZLSFGC-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- DNAPJAGHXMPFLD-UHFFFAOYSA-N triiodosilane Chemical compound I[SiH](I)I DNAPJAGHXMPFLD-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Pipe Accessories (AREA)
- Silicon Polymers (AREA)
Abstract
Comprising the formula (1) (A is-C (═ O) OR1、‑C(＝O)NR1 2、‑C(＝O)SR1and-P (═ O) (OR)1)2Any one of (1), R1Is hydrogen atom, alkyl group having 1 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms or aralkyl group having 7 to 30 carbon atoms, Y is organic group having 2 valence, R is alkyl group having 1 to 4 carbon atoms or phenyl group, R' is alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or aralkyl group having 7 to 30 carbon atoms20, p is 2 or 3, X is a hydroxyl group or a hydrolyzable group, and n is 1 to 3. ) The surface treatment agent of the organosilane compound and/or the partial (hydrolytic) condensate thereof can form a cured coating film which has excellent lipophilicity, a refractive index close to that of sebum, and excellent abrasion durability.
Description
Technical Field
The present invention relates to an organosilane compound or the like containing a hydroxyl group or a hydrolyzable group and an oleophilic group in a molecule, and more particularly to a lipophilic group-containing (hydrolyzable) organosilane compound forming a film having excellent lipophilicity, a surface treatment agent containing the lipophilic group-containing (hydrolyzable) organosilane compound and/or a partial (hydrolyzed) condensate thereof, and an article surface-treated with the surface treatment agent (that is, having a cured film of the surface treatment agent on the surface), and the like.
Background
In recent years, the touch panel of a screen has been accelerated, including a display of a mobile phone. However, the touch panel is exposed on the screen, and therefore, there is a large chance that fingers, cheeks, and the like are in direct contact with each other, and there is a problem that dirt such as sebum is likely to adhere to the touch panel. Therefore, in order to improve the appearance and visibility, a technique for making it difficult for fingerprints to adhere to the surface of a display and a technique for making dirt easily fall off have been increasingly demanded year by year, and development of materials that can satisfy these demands has been desired. In particular, since fingerprint stains (sebum stains) are likely to adhere to the surface of the touch panel display, it is desirable to provide an oil-repellent layer for making it difficult for sebum stains to adhere to the surface, and conversely, an oil-philic layer for making the sebum stains (fingerprints and the like) inconspicuous when the sebum stains such as fingerprints are adhered.
Generally, silane coupling agents are known as substances for bonding organic compounds to the surface of a substrate such as glass or cloth, and are widely used as coating agents for the surface of various substrates. The silane coupling agent has an organic functional group and a reactive silyl group (generally, a hydrolyzable silyl group such as an alkoxysilyl group) in 1 molecule, and the hydrolyzable silyl group undergoes a self-condensation reaction by moisture or the like in the air to form a coating film. The coating film is a strong coating film having durability by chemically and physically bonding the hydrolyzable silyl group to the surface of glass, metal, or the like.
Therefore, many compositions have been disclosed which are easily adhered to the surface of a base material by using a fluoropolyether group-containing polymer having a hydrolyzable silyl group introduced into a fluoropolyether group-containing compound, and which can form a coating film having water-and oil-repellency, stain-proofing property, and the like on the surface of the base material (patent documents 1 to 6: Japanese patent application laid-open Nos. 2008-534696, 2008-537557, 2012-072272, 2012-157856, 2013-136833, 201520152015-199906).
However, an oil-repellent layer produced using a conventional polymer containing a fluoropolyether group has a high oil repellency and an excellent soil-release property, but has a problem that sebum scatters light when fingerprints and the like are attached, and fingerprints are easily conspicuous.
Further, there is also disclosed a composition which is capable of forming a coating film having lipophilicity on a substrate surface while adhering to the substrate surface by using a silane compound having a hydrolyzable silyl group introduced into a lipophilic compound (patent document 7: Japanese patent laid-open No. 2001-353808).
However, the silane compound described in patent document 7 has a refractive index significantly higher than that of sebum of about 1.5, and although fingerprints are hard to be conspicuous, it cannot sufficiently exhibit low visibility of fingerprints.
Documents of the prior art
Patent document
Patent document 1: japanese Kokai publication No. 2008-534696
Patent document 2: japanese Kokai publication No. 2008-537557
Patent document 3: japanese laid-open patent publication No. 2012 and 072272
Patent document 4: japanese laid-open patent publication No. 2012-157856
Patent document 5: japanese patent laid-open publication No. 2013-136833
Patent document 6: japanese patent laid-open publication No. 2015-199906
Patent document 7: japanese laid-open patent publication No. 2001-353808
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lipophilic group-containing (hydrolyzable) organic silane compound, a surface treatment agent containing the lipophilic group-containing (hydrolyzable) organic silane compound and/or a partial (hydrolysis) condensate thereof, and an article or the like surface-treated with the surface treatment agent, wherein the lipophilic group-containing (hydrolyzable) organic silane compound can form a cured film having excellent lipophilicity, so that when a fingerprint or the like is adhered, the fingerprint is not easily visualized by sebum without scattering light, and the cured film can be formed in a structure having a refractive index close to that of sebum of about 1.5, so that low visibility of the fingerprint can be sufficiently exhibited, and the abrasion durability is excellent.
Means for solving the problems
In order to achieve the above object, the present inventors have developed a fingerprint low visibility silane compound having a refractive index of about 1.5 close to that of sebum in international publication No. 2019/082583.
However, the silane compound described in international publication No. 2019/082583 is not necessarily sufficient in wear durability, particularly durability when worn with a rubber, and a coating film may peel off, and therefore, the visibility of a fingerprint may be reduced with use.
Therefore, further studies were carried out, and as a result, it was found that: by using a (hydrolyzable) organosilane compound having a specific molecular structure represented by the general formula (1) described later, particularly a (hydrolyzable) organosilane compound having a specific molecular structure represented by the general formula (2) described later, as the (hydrolyzable) organosilane compound having a hydroxyl group or a hydrolyzable group and an oleophilic group, in the (hydrolyzable) organosilane compound having a specific molecular structure represented by the general formula (1) described later, a surface treatment agent containing the (hydrolyzable) organosilane compound having a lipophilic group and/or a partial (hydrolyzed) condensate thereof can form a cured coating film having excellent lipophilicity, a refractive index close to that of sebum, and excellent abrasion durability, and the present invention has been completed.
Accordingly, the present invention provides a lipophilic group-containing (hydrolyzable) organic silane compound, a surface treatment agent, an article, and the like described below.
[1] An organosilane compound represented by the following general formula (1).
[ solution 1]
(wherein A is-C (═ O) OR1、-C(＝O)NR1 2、-C(＝O)SR1and-P (═ O) (OR)1)2Any one of (1), R1The compound is hydrogen atom, alkyl with 1-30 carbon atoms, aryl with 6-30 carbon atoms or aralkyl with 7-30 carbon atoms, Y is independently organic group with 2 valence, R is independently alkyl with 1-4 carbon atoms or phenyl, R' is alkyl with 1-20 carbon atoms, aryl with 6-20 carbon atoms or aralkyl with 7-20 carbon atoms, p is 2 or 3, X is hydroxyl or hydrolytic group independently, and n is an integer of 1-3. )
[2] [1] the organosilane compound according to the formula (1), wherein Y is a C2-30 alkylene group which may contain a C2-C arylene group, or a group having a valence 2 selected from the group consisting of a silalkylene group, a silarylene group, and a linear, branched or cyclic 2-C organopolysiloxane residue having 2 to 10 silicon atoms.
[3] [1] the organosilane compound according to [1] or [2], wherein in the formula (1), X is independently selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom, an oximino group, an isocyanate group and an cyanate group.
[4] The organosilane compound represented by any one of [1] to [3], which is represented by the following formula (2).
[ solution 2]
(in the formula, R2Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, m is independently an integer of 2 to 20, R' is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, p is 2 or 3, and X is independently a hydroxyl group or a hydrolyzable group. )
[5] The organosilane compound according to any one of [1] to [4], wherein the refractive index is 1.45 or more.
[6] A surface-treating agent comprising at least 1 of the organosilane compounds and/or partial (hydrolytic) condensates thereof according to any one of [1] to [5 ].
[7] [6] the surface treatment agent, further comprising a solvent.
[8] The surface treating agent according to [6] or [7], which further comprises a hydrolytic condensation catalyst.
[9] The surface treatment agent according to any one of [6] to [8], which gives a cured film having an oleic acid contact angle of 30 ° or less at 25 ℃ and a relative humidity of 40%.
[10] The surface treatment agent according to any one of [6] to [9], which gives a cured film having a haze of 10 or less when sebum is adhered to the cured film with a load of 1 kg.
[11] [6] to [10], wherein a cured coating having a water contact angle of 50 ° or more after 2000 times of abrasion with a rubber is applied.
[12] An article having a cured coating of the surface treatment agent according to any one of [6] to [11] on the surface thereof.
[13] A method for adjusting the refractive index of a substrate surface to 1.45 to 1.52 according to JIS K0062, which comprises a step of forming a cured film of the surface treatment agent according to any one of [6] to [11] on the substrate surface.
ADVANTAGEOUS EFFECTS OF INVENTION
The (hydrolyzable) organic silane compound containing a lipophilic group of the present invention has a lipophilic terminal group in the molecule, and thus can wet and spread sebum on a substrate when sebum is attached, and can make the refractive index of the surface of a cured coating close to that of sebum (about 1.5) by containing a phenylene group. Thus, an article surface-treated with a surface-treating agent containing the (hydrolyzable) organosilane compound having a lipophilic group and/or a partial (hydrolytic) condensate thereof has a refractive index of 1.45 or more, particularly 1.45 to 1.52, based on JIS K0062 on the surface of the article, and therefore has excellent low-visibility of fingerprints (property of making attached fingerprints less noticeable). Further, the (hydrolyzable) organic silane compound containing a lipophilic group of the present invention has 2 or more (2 or 3) reactive terminal groups bonded to tertiary carbon atoms, and therefore, the adhesion to the substrate is improved and particularly excellent rubber wear durability is exhibited.
Detailed Description
The (hydrolyzable) organosilane compound containing a lipophilic group in the molecule of the present invention is represented by the following general formula (1), and may be a mixture.
[ solution 3]
(wherein A is-C (═ O) OR1、-C(＝O)NR1 2、-C(＝O)SR1and-P (═ O) (OR)1)2Any one of (1), R1The compound is hydrogen atom, alkyl with 1-30 carbon atoms, aryl with 6-30 carbon atoms or aralkyl with 7-30 carbon atoms, Y is independently organic group with 2 valence, R is independently alkyl with 1-4 carbon atoms or phenyl, R' is alkyl with 1-20 carbon atoms, aryl with 6-20 carbon atoms or aralkyl with 7-20 carbon atoms, p is 2 or 3, X is hydroxyl or hydrolytic group independently, and n is an integer of 1-3. )
The lipophilic group-containing (hydrolyzable) organic silane compound of the present invention has a structure in which a lipophilic terminal group is bonded to a hydrolyzable silyl group such as an alkoxysilyl group or a hydroxyl group-containing silyl group via a silylene group as a linking group, and is characterized by excellent adhesion to a substrate and lipophilicity.
In the formula (1), A is represented by-C (═ O) OR1Esters or carboxylic acids represented by-C (═ O) NR1 2An amide represented by-C (═ O) SR1A thioester of the formulaThioacid, and a compound of-P (═ O) (OR)1)2Any of the phosphonate esters or phosphonic acids represented herein is a lipophilic terminal group in the present invention.
Wherein R is1The alkyl group may be straight, branched or cyclic, and may be a combination of any of hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms and an aralkyl group having 7 to 30 carbon atoms. Preferably a linear alkyl group having 1 to 10 carbon atoms, more preferably a linear alkyl group having 2 to 8 carbon atoms.
As R1Specific examples thereof include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isopropyl group, isobutyl group, tert-butyl group, neopentyl group, 1, 2-trimethylpropyl group (テキシル group; texyl group), cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclohexylmethyl group, norbornyl group, decahydronaphthyl group, adamantyl group, adamantylmethyl group and other alkyl groups, phenyl group, tolyl group, naphthyl group and other aryl groups, benzyl group, phenylethyl group, phenylpropyl group and other aralkyl groups. As R1Preferably, ethyl and octyl are used.
Examples of a include the following groups.
[ solution 4]
[ solution 5]
In the formula (1), X is a hydroxyl group or a hydrolyzable group which may be different from each other. Examples of such X include hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy and other alkoxy groups having 1 to 10 carbon atoms, methoxymethoxy, methoxyethoxy and other alkoxy-substituted alkoxy groups having 2 to 10 carbon atoms, acetoxy and other acyloxy groups, isopropenoxy and other acyloxy groups having 1 to 10 carbon atoms, fluorine, chlorine, bromine, iodine and other halogen atoms, oximino, isocyanate, cyanate groups and the like. Among them, preferred are methoxy group, ethoxy group, isopropenyloxy group, and chlorine atom.
In the formula (1), R is an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like, or a phenyl group, and among them, a methyl group is preferable.
n is an integer of 1 to 3, preferably 2 or 3, and more preferably 3 from the viewpoint of reactivity and adhesion to a substrate.
In the formula (1), R' is alkyl with 1-20 carbon atoms, aryl with 6-20 carbon atoms or aralkyl with 7-20 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isopropyl, isobutyl, tert-butyl, neopentyl, 1, 2-trimethylpropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, norbornyl, decahydronaphthyl, adamantyl and other alkyl groups, phenyl, tolyl, naphthyl and other aryl groups, benzyl, phenylethyl, phenylpropyl, naphthylmethyl and other aralkyl groups. R' is preferably an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms or an aralkyl group having 7 to 15 carbon atoms, and more preferably a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a tetradecyl group, a phenyl group, a tolyl group, a naphthyl group, a benzyl group or a naphthylmethyl group.
In the formula (1), Y is a 2-valent organic group, is a linking group between the group A and the silylene group, and a linking group between the tertiary carbon atom and the hydrolyzable silyl group or the hydroxyl-containing silyl group, and preferably may contain a 2-valent group selected from the group consisting of a silylene group, a silylarylene group, and a linear, branched or cyclic 2-valent organopolysiloxane residue having 2 to 10 silicon atoms, and may further contain an alkylene group having 2 to 30 carbon atoms, particularly 2 to 20 carbon atoms, which may contain an arylene group having 6 to 20 carbon atoms, and more preferably a 2-valent group represented by the following formula (3).
-R3-Z-(R3)a- (3)
In the above formula (3), R3Independently of valence 2The hydrocarbon group includes, specifically, alkylene groups having 2 to 30 carbon atoms such as ethylene, propylene, butylene, and hexamethylene, alkylene-arylene groups having 7 to 30 carbon atoms including arylene groups having 6 to 20 carbon atoms such as phenylene, and preferably alkylene groups having 2 to 20 carbon atoms.
In the formula (3), Z is a single bond, a silylene group, a silylarylene group, or a 2-valent group selected from a linear, branched or cyclic 2-valent organopolysiloxane residue having 2 to 10, preferably 2 to 5 silicon atoms.
Examples of the silylene group and the silylene group include the following groups.
[ solution 6]
(in the formula, R4Is alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, etc., or aryl group having 6 to 10 carbon atoms such as phenyl group, R4May be the same or different. R5Is an alkylene group having 1 to 4 carbon atoms such as methylene, ethylene, propylene (trimethylene, methylethylene) or an arylene group having 6 to 10 carbon atoms such as phenylene. )
Examples of the linear, branched or cyclic 2-valent organopolysiloxane residue having 2 to 10, preferably 2 to 5 silicon atoms include the following groups.
[ solution 7]
(in the formula, R4As described above. g is an integer of 1 to 9, preferably 1 to 4, and h is an integer of 1 to 8, preferably 2 to 4. )
In the formula (3), a is 0 or 1.
Specific examples of Y include the following groups.
[ solution 8]
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2-
[ solution 9]
Examples of the lipophilic group-containing (hydrolyzable) organosilane compound represented by the formula (1) include compounds represented by the following formulae.
[ solution 10]
[ solution 11]
[ solution 12]
[ solution 13]
[ solution 14]
[ solution 15]
[ solution 16]
The lipophilic group-containing (hydrolyzable) organosilane compound of the present invention is more preferably a compound represented by the following general formula (2).
[ solution 17]
(in the formula, R2Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, m is independently an integer of 2 to 20, preferably 3 to 10, and R', p and X are the same as described above. )
Wherein R is2The alkyl group is preferably a C1-20 alkyl group, an aryl group is preferably a C6-20 aryl group, or an aralkyl group is preferably a C7-20 aralkyl group, more preferably a C1-10 linear alkyl group, and still more preferably a C2-8 linear alkyl group.
As R2Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isopropyl, isobutyl, tert-butyl, neopentyl, 1, 2-trimethylpropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylmethyl, norbornyl, decahydronaphthyl, adamantyl and other alkyl groups, phenyl, tolyl, naphthyl and other aryl groups, benzyl, phenylethyl, phenylpropyl and other aralkyl groups. As R2Preferably ethyl, butyl or octyl.
Examples of the (hydrolyzable) organosilane compound containing a lipophilic group represented by the above formula (2) include compounds represented by the following formula.
[ solution 18]
Examples of the method for producing the lipophilic group-containing (hydrolyzable) organosilane compound represented by the above formula (1), particularly the lipophilic group-containing (hydrolyzable) organosilane compound in which Y as a linking group between the group a and the silylene group in the formula (1) (that is, Y adjacent to the group a in the formula (1)) and Y as a linking group between the tertiary carbon atom and the hydrolyzable silyl group or the hydroxyl group-containing silyl group are alkylene groups having 2 to 20 carbon atoms.
A compound having A and phenyldimethylsilyl moieties and at least 2 olefinic moieties (e.g., alkenyl groups) of the above formula (1) at the molecular chain ends and an organosilicon compound having SiH groups and hydrolyzable end groups in the molecule, such as trimethoxysilane, are allowed to cure in the presence of a hydrosilylation catalyst, such as a toluene solution of chloroplatinic acid/vinylsiloxane complex, at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃, for 10 minutes to 48 hours, preferably 1 to 36 hours, more preferably about 24 hours. In addition, the reaction may be carried out by diluting with an organic solvent.
Among them, as the compound having a and phenyldimethylsilyl moieties and at least 2 olefin moieties (for example, alkenyl groups) in the above formula (1) at the molecular chain end, silane compounds represented by the following general formulae (4a), (4b), (4c), (4d) and (4e) can be exemplified.
[ solution 19]
(wherein R' and R1M is the same as above, and m' is an integer of 0 to 18. )
As the silane compound represented by the formula (4a), specifically, the following compounds can be exemplified.
[ solution 20]
[ solution 21]
[ solution 22]
As the silane compound represented by the formula (4b), specifically, the following compounds can be exemplified.
[ solution 23]
As the silane compound represented by the formula (4c), specifically, the following compounds can be exemplified.
[ solution 24]
As the silane compound represented by the formula (4d), specifically, the following compounds can be exemplified.
[ solution 25]
As the silane compound represented by the formula (4e), specifically, the following compounds can be exemplified.
[ solution 26]
As a method for producing the silane compounds represented by the above-mentioned formulas (4a), (4b), (4c), (4d) and (4e), first, compounds each having a hydroxyl group and at least 2 olefin sites (e.g., alkenyl groups) are mixed with a dehydrogenation catalyst. Subsequently, a compound having a silane compound having a and a phenyldimethylsilyl moiety of the formula (1) at the molecular chain end (for example, dimethylsilane having a and a dimethylhydrosilylphenyl group of the formula (1) at the molecular chain end as a substituent bonded to a silicon atom) is dropped and stirred at a temperature of 0 to 60 ℃, preferably 15 to 50 ℃, more preferably about 30 ℃, and then aged for 10 minutes to 24 hours, preferably 30 minutes to 2 hours, more preferably 1 hour. In addition, the reaction may be carried out by diluting with an organic solvent.
Examples of the silane compound having a and a phenyldimethylsilyl moiety in the formula (1) at the molecular chain terminal in the preparation of the silane compounds represented by the formulae (4a), (4b), (4c), (4d) and (4e) include silane compounds represented by the following general formulae (4a '), (4 b'), (4c ') and (4 d').
[ solution 27]
(in the formula, R1And m is the same as described above. )
As the silane compound represented by the formula (4 a'), specifically, the following compounds can be exemplified.
[ solution 28]
[ solution 29]
[ solution 30]
As the silane compound represented by the formula (4 b'), specifically, the following compounds can be exemplified.
[ solution 31]
As the silane compound represented by the formula (4 c'), specifically, the following compounds can be exemplified.
[ solution 32]
As the silane compound represented by the formula (4 d'), specifically, the following compounds can be exemplified.
[ solution 33]
As the preparation method of the silane compound represented by the above formulas (4a '), (4 b'), (4c ') and (4 d'), 1, 4-bis (dimethylsilyl) benzene is heated and stirred at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃, and a hydrosilylation catalyst such as a toluene solution of chloroplatinic acid/vinylsiloxane complex is added. Then, the compound having a and an olefin site (e.g., alkenyl group) in the formula (1) at the molecular chain terminal is slowly dropped over a long period of time, and then cured at a temperature of 40 to 120 ℃, preferably 60 to 100 ℃, more preferably about 80 ℃ for 10 minutes to 12 hours, preferably 1 to 6 hours, more preferably 3 to 6 hours. In addition, the reaction may be carried out by diluting with an organic solvent.
Specific examples of the compound having a and an olefin moiety in the formula (1) at the molecular chain terminal include the compounds shown below.
[ chemical 34]
C2H5OOC-(CH2)2-CH＝CH2
C2H5OOC-(CH2)8-CH＝CH2
C2H5OOC-(CH2)11-CH＝CH2
H3COOC-(CH2)8-CH＝CH2
C4H9OOC-(CH2)8-CH＝CH2
C8H17OOC-(CH2)8-CH＝CH2
[ solution 35]
(C2H5)2NOC-(CH2)2-CH＝cH2
(C2H5)2NOC-(CH2)8-CH＝CH2
(C4H9)2NOC-(CH2)2-CH＝CH2
(C4H9)2NOC-(CH2)a-CH＝CH2
C2H5SOC-(CH2)2-CH＝CH2
C2H5SOC-(CH2)8-CH＝CH2
C4H9SOC-(CH2)2-CH＝CH2
C4H9SOC-(CH2)8-CH＝CH2
C8H17SOC-(CH2)8-CH＝CH2
(H3CO)2POC-(CH2)2-CH＝CH2
(H3CO)2POC-(CH2)8-CH＝CH2
(C2H5O)2POC-(CH2)2-CH＝CH2
(C2H5O)2POC-(CH2)8-CH＝CH2
The amount of the compound having a and an olefin moiety in the formula (1) at the molecular chain end can be 0.05 to 0.5 equivalent, more preferably 0.1 to 0.4 equivalent, and still more preferably about 0.2 equivalent, to 1 equivalent of 1, 4-bis (dimethylsilyl) benzene.
In the preparation of the silane compounds represented by the above formulae (4a '), (4 b'), (4c ') and (4 d'), examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified products of chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols and the like, and platinum group metal-based catalysts such as tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) rhodium chloride and the like. Preferred are platinum group compounds such as vinylsiloxane complex.
The amount of the hydrosilylation catalyst used is 0.001 to 100ppm, more preferably 0.005 to 50ppm, in terms of transition metal (mass), based on the total mass of 1, 4-bis (dimethylsilyl) benzene and the compound having a and an olefin site in the above formula (1) at the molecular chain terminal.
An organic solvent may be used in the preparation of the silane compounds represented by the above formulae (4a '), (4 b'), (4c ') and (4 d'). Examples of the organic solvent to be used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, and the like) and hydrocarbon solvents (petroleum spirit, toluene, xylene, and the like). Among these, toluene is particularly preferable.
When a solvent is used, the amount of the solvent used can be 10 to 300 parts by mass, preferably 50 to 150 parts by mass, and more preferably about 100 parts by mass, per 100 parts by mass of the compound having a and an olefin site in the above formula (1) at the molecular chain terminal.
Subsequently, the reaction was stopped, and the solvent was distilled off to obtain silane compounds represented by the above formulae (4a '), (4 b'), (4c ') and (4 d').
Examples of the compounds having a hydroxyl group and at least 2 olefin sites (for example, alkenyl groups) in the production of the silane compounds represented by the above formulae (4a), (4b), (4c), (4d) and (4e) include compounds represented by the following general formulae (5) and (6).
[ solution 36]
(wherein R 'and m' are the same as defined above.)
As the compound represented by the formula (5), specifically, the following compounds can be exemplified.
[ solution 37]
[ solution 38]
As the compound represented by the formula (6), specifically, the following compounds can be exemplified.
[ solution 39]
As a method for producing a compound having a hydroxyl group and at least 2 olefin sites (for example, an alkenyl group) in the production of a silane compound represented by the above formulae (4a), (4b), (4C), (4d) and (4e), for example, a compound having an ester group (-C (═ O) -OR) in the molecule, a grignard reagent as a nucleophile and, for example, tetrahydrofuran as a solvent are mixed and aged at 0 to 80 ℃, preferably 10 to 30 ℃, more preferably about 25 ℃ for 1 to 6 hours, preferably 3 to 5 hours, more preferably about 4 hours.
Among them, as the compound to be used as a raw material, an acid halide, an acid anhydride, a carboxylic acid, an amide, and the like can be used as a group having in the molecule in addition to the above-mentioned ester.
Specific examples of the compound having these groups in the molecule include the compounds shown below.
[ solution 40]
(wherein R 'and m' are the same as defined above.)
As the nucleophilic agent used in the preparation of the compound having a hydroxyl group and at least 2 olefin sites (e.g., alkenyl group) in the preparation of the silane compound represented by the above-mentioned formulae (4a), (4b), (4c), (4d), and (4e), respectively, allyl magnesium halide, 3-butenyl magnesium halide, 4-pentenyl magnesium halide, 5-hexenyl magnesium halide, and the like can be used. In addition, corresponding lithium reagents can also be used.
The amount of the nucleophilic agent to be used may be 2 to 5 equivalents, more preferably 2.5 to 3.5 equivalents, and still more preferably about 3 equivalents, based on 1 equivalent of the above-mentioned compound.
As the solvent used for the preparation of the compound having a hydroxyl group and at least 2 olefin sites (for example, an alkenyl group) in the preparation of the silane compound represented by the above formulae (4a), (4b), (4c), (4d) and (4e), ether solvents such as Tetrahydrofuran (THF), monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and dioxane can be used as the organic solvent.
The amount of the solvent used may be 10 to 1000 parts by mass, preferably 50 to 500 parts by mass, and more preferably about 100 to 300 parts by mass, based on 100 parts by mass of the compound having an ester group in a molecule.
Subsequently, the reaction was stopped, and the aqueous layer and the organic layer were separated by a liquid separation operation. The obtained organic layer is washed and the solvent is distilled off, thereby obtaining compounds having a hydroxyl group and at least 2 olefin sites (for example, alkenyl groups) in the production of the silane compounds represented by the above formulae (4a), (4b), (4c), (4d) and (4 e).
In the preparation of the silane compounds represented by the above formulas (4a), (4b), (4c), (4d) and (4e), the amount of the silane compound having a and a phenyldimethylsilyl moiety in the above formula (1) at the molecular chain end is 0.8 to 1.2 equivalents, more preferably 0.9 to 1.1 equivalents, and further preferably about 1 equivalent, relative to 1 equivalent of the compound having a hydroxyl group and at least 2 olefin moieties (e.g., alkenyl groups).
In the preparation of the silane compounds represented by the above formulae (4a), (4b), (4c), (4d) and (4e), as the dehydrogenation catalyst, for example, a platinum group metal-based catalyst such as rhodium, palladium and ruthenium, a boron catalyst and the like can be used, and specific examples thereof include platinum group metal-based catalysts such as tetrakis (triphenylphosphine) palladium and tris (triphenylphosphine) rhodium chloride, a boron catalyst such as tris (pentafluorophenyl) borane and the like.
The amount of the dehydrogenation catalyst used may be 0.01 to 0.0005 equivalent, more preferably 0.007 to 0.0003 equivalent, and still more preferably about 0.001 equivalent, to 1 equivalent of the compound having a hydroxyl group and at least 2 olefin sites (e.g., alkenyl groups) in the preparation of the silane compound represented by the formulae (4a), (4b), (4c), (4d), and (4 e).
An organic solvent may be used in the preparation of the silane compounds represented by the above-described formulae (4a), (4b), (4c), (4d) and (4 e). Examples of the organic solvent to be used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, and the like) and hydrocarbon solvents (petroleum spirit, toluene, xylene, and the like). Among these, toluene is particularly preferable.
The amount of the organic solvent used may be 10 to 300 parts by mass, preferably 10 to 250 parts by mass, and more preferably about 200 parts by mass, based on 100 parts by mass of the compound having a hydroxyl group and at least 2 olefin sites (e.g., alkenyl groups) in the production of the silane compound represented by the above formulae (4a), (4b), (4c), (4d), and (4 e).
In the preparation of the silane compounds represented by the above formulae (4a), (4b), (4c), (4d) and (4e), a fluorine-based solvent may be added. Examples of the fluorine-containing solvent to be used include a fluorine-containing aromatic hydrocarbon solvent such as 1, 3-bis (trifluoromethyl) benzene and trifluoromethylbenzene, a Hydrofluoroether (HFE) solvent such as 1,1, 1,2, 3, 4, 4, 5, 5, 5-decafluoro-3-methoxy-2- (trifluoromethyl) pentane (trade name: Novec series, manufactured by 3M Co.), a perfluoro-based solvent composed of a completely fluorinated compound (trade name: FLORINATE series, manufactured by 3M Co.), and the like.
The amount of the fluorine-based solvent used may be 10 to 300 parts by mass, preferably 30 to 100 parts by mass, and more preferably about 60 parts by mass, based on 100 parts by mass of the compound having a hydroxyl group and at least 2 olefin sites (for example, alkenyl groups) in the production of the silane compound represented by the above formulae (4a), (4b), (4c), (4d), and (4 e).
Then, the reaction is stopped, and the solvent is distilled off, thereby obtaining a compound having a and phenyldimethylsilyl moieties and at least 2 olefin moieties (e.g., alkenyl groups) in the above formula (1) at the molecular chain end.
Among these, the organosilicon compounds having an SiH group and a hydrolyzable terminal group in the molecule are preferably compounds represented by the following general formulae (7) to (10).
[ solution 41]
(wherein R, X, n, R3、R4、R5G is the same as above, i is an integer of 2 to 9, preferably 2 to 4, j is an integer of 0 to 8, preferably 0 or 1, and i + j is an integer of 2 to 9. )
Examples of the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule include trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisopropenoxysilane, triacetoxysilane, trichlorosilane, tribromosilane, triiodosilane, and the following silanes.
[ solution 42]
In the formula (1), the amount of the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule is 2 to 8 equivalents, more preferably 3 to 5 equivalents, and still more preferably about 4 equivalents, to 1 equivalent of the compound having a and a phenyldimethylsilyl group site and at least 2 olefin sites (for example, alkenyl groups) in the formula (1) at the molecular chain end.
In the preparation of the lipophilic group-containing (hydrolyzable) organosilane compound represented by the above formula (1), examples of the hydrosilylation reaction catalyst include platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, and the like, and platinum group metal-based catalysts such as tetrakis (triphenylphosphine) palladium, tris (triphenylphosphine) rhodium chloride, and the like. Preferred are platinum group compounds such as vinylsiloxane complex.
The hydrosilylation catalyst is used in an amount of 0.1 to 100ppm, more preferably 0.5 to 50ppm, in terms of transition metal (mass), based on the total mass of the compound having a and phenyldimethylsilyl moieties and at least 2 olefin moieties (e.g., alkenyl groups) in the formula (1) at the molecular chain end and the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, such as trimethoxysilane.
An organic solvent can be used for the preparation of the lipophilic group-containing (hydrolyzable) organosilane compound represented by the above formula (1). Examples of the organic solvent to be used include ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, and the like) and hydrocarbon solvents (petroleum spirit, toluene, xylene, and the like). Among these, toluene is particularly preferable.
The amount of the organic solvent used is 10 to 300 parts by mass, preferably 15 to 100 parts by mass, and more preferably about 20 parts by mass, per 100 parts by mass of the compound having a and a phenyldimethylsilyl group and at least 2 olefin groups (for example, alkenyl groups) in the formula (1) at the molecular chain end.
Then, the reaction is stopped, and the solvent and unreacted components are removed by fractional distillation, whereby a lipophilic group-containing (hydrolyzable) organosilane compound represented by the above formula (1) is obtained.
For example, as the compound having a and phenyldimethylsilyl moieties and at least 2 olefin moieties (e.g., alkenyl groups) in the above formula (1) at the molecular chain end, a compound represented by the following formula is used
[ solution 43]
When trimethoxysilane is used as the organosilicon compound having an SiH group and a hydrolyzable terminal group in the molecule, a compound represented by the following formula is obtained.
[ solution 44]
Since the lipophilic group-containing (hydrolyzable) organic silane compound represented by the above formula (1) has a specific molecular structure and has a refractive index of 1.45 or more, particularly 1.46 to 1.52 measured according to JIS K0062, a cured film having a refractive index of 1.45 or more, particularly 1.46 to 1.52 can be formed, while the refractive index of sebum is usually about 1.5, the refractive index of the cured film of the lipophilic group-containing (hydrolyzable) organic silane compound is brought closer to the refractive index of sebum, so that sebum can be made inconspicuous.
The present invention also provides a surface treatment agent containing the above-mentioned (hydrolyzable) organosilane compound containing a lipophilic group and/or a partial (hydrolytic) condensate thereof. The surface treatment agent can use 1 kind of lipophilic group-containing (hydrolyzable) organosilane compound alone, or 2 or more kinds of compounds in combination, or can use 1 kind of compound alone or 2 or more kinds of compounds in combination with a lipophilic group-containing (hydrolyzable) organosilane compound alone, or a partial hydrolytic condensate obtained by condensing a hydroxyl group obtained by partially hydrolyzing the terminal hydrolyzable group of the lipophilic group-containing hydrolyzable organosilane compound in advance by a known method, or a partial hydrolytic condensate obtained by partially hydrolyzing the terminal hydrolyzable group of the lipophilic group-containing hydrolyzable organosilane compound in advance.
The surface treatment agent may comprise a suitable solvent. Examples of such a solvent include alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), ether solvents (dibutyl ether, diethyl ether, tetrahydrofuran, etc.), hydrocarbon solvents (petroleum spirit, toluene, xylene, etc.), and ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these, alcohol-based solvents and ether-based solvents are preferable in terms of solubility, wettability, and the like, and propylene glycol monomethyl ether and dibutyl ether are particularly preferable.
The solvent may be a mixture of 2 or more kinds thereof, and preferably the (hydrolyzable) organosilane compound containing a lipophilic group and a partial (hydrolyzed) condensate thereof are uniformly dissolved. The optimum concentration of the lipophilic group-containing (hydrolyzable) organosilane compound and its partial (hydrolyzed) condensate dissolved in the solvent varies depending on the treatment method, and may be an amount that can be easily weighed, and in the case of direct application, the concentration is preferably 0.01 to 10 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total of the solvent and the lipophilic group-containing (hydrolyzable) organosilane compound (and its partial (hydrolyzed) condensate), and in the case of vapor deposition treatment, the concentration is preferably 1 to 100 parts by mass, and particularly preferably 3 to 30 parts by mass, relative to 100 parts by mass of the total of the solvent and the lipophilic group-containing (hydrolyzable) organosilane compound (and its partial (hydrolyzed) condensate), preferably 0.01 to 10 parts by mass, and particularly preferably 0.05 to 1 part by mass.
The surface treatment agent may contain a hydrolytic condensation catalyst, for example, an organic tin compound (e.g., dibutyl dimethoxy tin, dibutyl tin dilaurate, etc.), an organic titanium compound (e.g., tetra-n-butyl titanate, etc.), an organic acid (e.g., acetic acid, methanesulfonic acid, etc.), and an inorganic acid (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, etc.). Among these, acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate and the like are particularly preferable.
The amount of the hydrolytic condensation catalyst to be added is preferably 0.1 to 150 parts by mass, particularly preferably 25 to 125 parts by mass, and further preferably 50 to 110 parts by mass, based on 100 parts by mass of the (hydrolyzable) organosilane compound containing a lipophilic group and/or its partial (hydrolytic) condensate.
The surface treatment agent of the present invention can be applied to a substrate by a known method such as brush coating, dipping, spraying, or vapor deposition. The heating method in the vapor deposition treatment may be a resistance heating method or an electron beam heating method, and is not particularly limited. The curing temperature varies depending on the curing method, and for example, in the case of direct coating (brush coating, dipping, spraying, etc.), it is preferably carried out at 25 to 200 ℃, particularly 25 to 150 ℃, for 15 minutes to 36 hours, particularly 30 minutes to 24 hours. It may be allowed to solidify under humidification. When the vapor deposition treatment is applied, the temperature is preferably in the range of 20 to 200 ℃. It may be allowed to solidify under humidification. The thickness of the cured coating is suitably selected depending on the type of the substrate, and is usually 0.1 to 100nm, particularly 1 to 20 nm. For example, in the case of spray coating, when spray coating is performed after dilution in an organic solvent to which moisture has been added in advance and hydrolysis, i.e., after Si — OH is generated, curing after coating is fast.
The surface treatment agent of the present invention can form a cured coating film having a contact angle to oleic acid of preferably 30 ° or less, more preferably 25 ° or less, at 25 ℃ and a relative humidity of 40%, as measured by a contact angle meter Drop Master (manufactured by union interface science). Therefore, when sebum adheres, the contact angle is small, visibility is reduced, and fingerprints are not conspicuous. In this case, the oleic acid contact angle changes with time and converges to a constant value after 40 seconds, and therefore the value after 40 seconds is taken as the oleic acid contact angle in the present invention.
The surface treatment agent of the present invention can form a cured film having a haze of 10 or less, more preferably 7 or less, as measured by a haze meter NDH5000 (manufactured by japan electro-chromo industries, ltd.) when sebum is adhered with a load of 1 kg. Therefore, when sebum adheres, the haze is small, the visibility is reduced, and the fingerprint is not conspicuous.
The surface treatment agent of the present invention can form a cured film having a contact angle (water repellency) to water of 50 ° or more after rubbing 2000 times under the following conditions using a rubbing tester (manufactured by new eastern science corporation). Therefore, the durability of the cured coating can be maintained when the cured coating is rubbed with a finger.
Resistance to wear of rubber
Rubber: manufactured by Minoan corporation
Contact area: 6mm phi
Travel distance (single pass): 30mm
Moving speed: 3600 mm/min
Loading: 1kg/6mm phi
The substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and may be various materials such as paper, cloth, metal and its oxide, glass, plastic, ceramic, and quartz. The surface treatment agent of the present invention can impart lipophilicity to the base material. In particular, it can be suitably used as SiO 22The surface treatment agent for glass and film to be treated is used.
Examples of the article treated with the surface treatment agent of the present invention include medical devices such as car navigation systems, cellular phones, smart phones, digital cameras, digital video cameras, PDAs, portable audio players, car audios, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastroscopes, and optical articles such as copiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films. The surface treatment agent of the present invention is hardly visible even if fingerprints and sebum adhere to the above-mentioned articles, and is particularly useful as an oleophilic layer for touch panel displays, antireflection films, and the like.
An article surface-treated with the surface treatment agent of the present invention has a refractive index of 1.45 or more, preferably 1.45 to 1.52, particularly 1.47 to 1.50, in accordance with JIS K0062, on the surface of a base material of the article, and therefore has excellent low-visibility fingerprint.
Examples
The present invention will be described in more detail below by way of examples and comparative examples, but the present invention is not limited to the following examples.
[ example 1]
45.7g (2.35X 10) of 1, 4-bis (dimethylsilyl) benzene placed in a reaction vessel-1mol) are heated to 80 ℃. Next, a 1.0X 10 toluene solution to which chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol) later, over 3 hours10.0g (4.71X 10) of ethyl undecylenate is added dropwise-2mol), heated and stirred at 80 ℃ for 3 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure, whereby 18.0g of a compound represented by the following formula (A) was obtained.
[ solution 45]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ1.2-1.5(-(C 2H)7-，-OCH2C 3H)17H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.3(-OOC-C 2H-)2H
δ4.1(-OC 2HCH3)2H
δ4.4(-Si-H)1H
δ7.5(-Si-C6 4H-Si-)4H
948ml (9.48X 10) of allyl magnesium chloride was placed in a reaction vessel-1mol: 1M/THF (tetrahydrofuran) solution) was cooled to 8 ℃. Subsequently, 50g (3.16X 10) of methyl octanoate diluted with THF100g was added dropwise-1mol), stirred at room temperature (25 ℃ C.) for 4 hours. Then, 500g of a 2.4M aqueous hydrochloric acid solution was added dropwise to the solution to stop the reaction. After the organic layer as the upper layer was collected by a liquid separation operation, the remaining solvent was distilled off under reduced pressure to obtain 66.0g of a compound represented by the following formula (B).
[ solution 46]
1H-NMR
δ0.8-0.9(-CH2-(CH2)5-C 3H)3H
δ1.2-1.3(-CH2-(C 3H)5-CH3)10H
δ1.4-1.5(-C 2H-(CH2)5-CH3)2H
δ2.2((-C 2H-CH＝CH2)2)4H
δ5.1((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
In a reaction vessel, a catalyst represented by the following formula (B)
[ solution 47]
5.00g (2.38X 10) of the compound shown-2mol), 10.0g of toluene, 3.00g of PF5060 (fluorine-based inactive solvent FLORINATE series, 3M Co., Ltd.), and 12.0mg (2.35X 10) of tris (pentafluorophenyl) borane-5mol) at room temperature. Then, the solution was slowly dropped into the reaction vessel represented by the following formula (A)
[ solution 48]
The compound (9.70 g) (2.38X 10)-2mol), stirred at 30 ℃ for 1 hour. Then, PF5060 was added, the lower fluorine layer was removed by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 14.5g of a compound represented by the following formula (C).
[ solution 49]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-CH3)3H
δ1.1-1.3(-(C 2H)7-，-OCH2C 3H，-CH2-(C 2H)5-CH3)27H
δ1.4-1.5(-C 2H-(C 2H)5-CH3)2H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-OOC-C 2H-)6H
δ4.1(-OC 2HCH3)2H
δ5.0((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel containing a catalyst represented by the following formula (C)
[ solution 50]
10.0g (1.63X 10) of the compound shown-2mol), 2.00g of toluene, heated to 80 ℃. Next, a 1.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 7.95g (6.52X 10) of trimethoxysilane-2mol), and aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 11.7g of a liquid compound.
By passing1H-NMR confirmed the obtained compoundThe product is a hydrolyzable organosilane compound 1 containing a lipophilic group represented by the following formula (D).
[ solution 51]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CH2CH2C 2H-Si(-OCH3)3)4H
δ0.7(-(CH2)7C 2H-Si-)2H
δO.8-0.9(-CH2-(CH2)5-C 3H)3H
δ1.1-1.5(-(C 2H)7-，-OCH2C 3H，-C 2H-(C 2H)5-CH3，-C 2HC 2HCH2-Si(-OCH3)3)37H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3(-OOC-C 2H-)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)18H
δ4.1(-OC 2HCH3)2H
δ7.5(-Si-C6 4H-Si-)4H
[ example 2]
805ml (8.05X 10) of allyl magnesium chloride was placed in a reaction vessel-1mol: 1M/THF solution) was cooled to 8 ℃. Subsequently, 50g (2.68X 10) of methyl decanoate diluted with THF100g was added dropwise-1mol), stirred at room temperature for 4 hours. Then, 500g of a 2.4M aqueous hydrochloric acid solution was added dropwise to the solution to stop the reaction. The organic layer as the upper layer was collected by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 61.0g of a solution represented by the following formula (E)) The compound shown in the specification.
[ solution 52]
1H-NMR
δ0.8-0.9(-CH2-(CH2)7-C 3H)3H
δ1.2-1.3(-CH2-(C 2H)7-CH3)14H
δ1.4-1.5(-C 2H-(CH2)7-CH3)2H
δ2.2((-C 2H-CH＝CH2)2)4H
δ5.1((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
Placing a reaction vessel containing a catalyst represented by the following formula (E)
[ Hua 53]
10.6g (4.46X 10) of the compound shown-2mol), 20.0g of toluene, PF50606.00g, 22.8mg (4.46X 10) of tris (pentafluorophenyl) borane-5mol) at room temperature. Then, the solution was slowly dropped into the reaction vessel represented by the following formula (A)
[ solution 54]
The compound (D) is 18.1g (4.46X 10)-2mol), stirred at 30 ℃ for 1 hour. Then, PF5060 was added, the lower fluorine layer was removed by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 27.7g of a compound represented by the following formula (F).
[ solution 55]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)7-C 3H)3H
δ1.1-1.3(-(C 2H)7-，-OCH2C 3H，-CH2-(C 2H)7-CH3)31H
δ1.4-1.5(-C 2H-(C 2H)7-CH3)2H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-OOC-C 2H-)6H
δ4.1(-OC 2HCH3)2H
δ5.0((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel containing a catalyst represented by the following formula (F)
[ solution 56]
The compound (D) was 20.0g (3.11X 10)-2mol), toluene 4.00g, heated to 80 ℃. Next, a 2.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex was added-2g (in Pt form)A mass meter comprising 1.3X 10-6mol), 15.2g (1.25X 10) of trimethoxysilane-1mol), and aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 22.0g of a liquid compound.
By using1H-NMR confirmed that the obtained compound was a hydrolyzable organosilane compound 2 containing a lipophilic group represented by the following formula (G).
[ solution 57]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CH2CH2C 2H-Si(-OCH3)3)4H
δ0.7(-(CH2)7C 2H--Si-)2H
δ0.8-0.9(-CH2-(CH2)7-C 3H)3H
δ1.1-1.5(-(C 2H)7-，-OCH2C 3H，-C 2H-(C 2H)7-CH3，-C 2HC 2HCH2-Si(-OCH3)3)41H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3(-OOC-C 2H-)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)18H
δ4.1(-OC 2HCH3)2H
δ7.5(-Si-C6 4H-Si-)4H
[ example 3]
300ml (3.00X 10) of allylmagnesium chloride was placed in a reaction vessel-1mol: 1M/THF solution) was cooled to 8 ℃. Then, a phenyl group diluted with THF30g was added dropwise15g of methyl acetate (1.00X 10)-1mol), stirred at room temperature for 4 hours. Then, 200g of a 2.4M aqueous hydrochloric acid solution was added dropwise to the solution to stop the reaction. After the organic layer as the upper layer was recovered by a liquid separation operation, the remaining solvent was distilled off under reduced pressure to obtain 17.0g of a compound represented by the following formula (H).
[ solution 58]
1H-NMR
δ2.2((-C 2H-CH＝CH2)2)4H
δ2.8(-C 2H-C6H5)2H
δ5.1((-CH2-CH＝C 2H)2)4H
δ5.9((-CH2-CH＝CH2)2)2H
δ7.2-7.3(-CH2-C6 5H)5H
Placing a reaction vessel containing a catalyst represented by the following formula (H)
[ chemical 59]
10.0g (4.95X 10) of the compound shown-2mol), 20.0g of toluene, PF50606.00g, 25.3mg (4.95X 10) of tris (pentafluorophenyl) borane-5mol) at room temperature. Then, the solution was slowly dropped into the reaction vessel represented by the following formula (A)
[ solution 60]
The compound represented by (20.1 g) (4.95X 10)-2mol), stirred at 30 ℃ for 1 hour. Then, PF5060 was added, and fluorine as a lower layer was separated by a liquid separation operationAfter the layer was removed, the remaining solvent was distilled off under reduced pressure to obtain 29.5g of a compound represented by the following formula (I).
[ solution 61]
1H-NMR
δ0.2-0.4(-Si-CH 3)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ1.1-1.3(-(C 2H)7-，-OCH2C 3H)17H
δ1.6(-OOC-CH2C 3H(CH2)7CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-OOC-C 3H-)6H
δ2.8(-C 2H-C6H5)2H
δ4.1(-OC 2HCH3)2H
δ5.1((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
δ7.2-7.3(-CH2-C6 5H)5H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel with a catalyst composed of the following formula (I)
[ solution 62]
10.0g (1.65X 10) of the compound represented-2mol), 2.00g of toluene, heated to 80 ℃. Next, a 1.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 8.00g (6.60X 10) of trimethoxysilane-2) mol), and aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 11.2g of a liquid compound.
By using1H-NMR confirmed that the obtained compound was a hydrolyzable organosilane compound 3 containing a lipophilic group represented by the following formula (J).
[ solution 63]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CH2CH2C 2H-Si(-OCH3)3)4H
δ0.7(-(CH2)7C 2H-Si-)2H
δ1.1-1.5(-(C 2H)7-，-OCH2C 3H，-C 2HCH 2CH2-Si(-OCH3)3)25H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3(-OOC-C 2H-)2H
δ2.8(-C 2H-C6H5)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)18H
δ4.1(-OC 2HCH3)2H
δ7.2-7.3(-CH2-C6 5H)5H
δ7.4(-Si-C6 4H-Si-)4H
[ example 4]
422ml (4.22X 10) of allyl magnesium chloride was placed in a reaction vessel-1mol: 1M/THF solution) was cooled to 8 ℃. Then, dropping20g (1.41X 10) of tert-butyl 3-butenoate diluted with THF30g were added-1mol), stirred at room temperature for 4 hours. Then, 250g of a 2.4M aqueous hydrochloric acid solution was added dropwise to the solution to stop the reaction. After the organic layer as the upper layer was collected by a liquid separation operation, the remaining solvent was distilled off under reduced pressure to obtain 18.0g of a compound represented by the following formula (K).
[ solution 64]
1H-NMR
δ2.2((-C 2H-CH＝CH2)2)6H
δ5.1((-CH2-CH＝C 2H)2)6H
δ5.9((-CH2-CH＝CH2)2)3H
Placing a reaction vessel containing a catalyst represented by the formula (K)
[ solution 65]
5.00g (3.29X 10) of the compound shown-2mol), 10.0g of toluene, PF50603.00g, 16.8mg of tris (pentafluorophenyl) borane (3.29X 10)-5mol) at room temperature. Then, the solution was slowly dropped into the reaction vessel represented by the following formula (A)
[ solution 66]
The compound represented by (13.4 g) (3.29X 10)-2mol), stirred at 30 ℃ for 1 hour. Then, PF5060 was added, the lower fluorine layer was removed by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 17.5g of a compound represented by the following formula (L).
[ solution 67]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ1.1-1.3(-(C 2H)7-，-OCH2C 3H)17H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-OOC-C 2H-)8H
δ4.1(-OC 2HCH3)2H
δ5.1((-CH2-CH＝C 2H)2)6H
δ5.8((-CH2-CH＝CH2)2)3H
δ7.2-7.3(-CH2-C6 5H)5H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel containing a catalyst represented by the following formula (L)
[ solution 68]
10.0g (1.80X 10) of the compound represented-2mol), 2.00g of toluene, heated to 80 ℃. Next, a 1.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 8.78g (7.20X 10) of trimethoxysilane-2) mol), aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 11.0g of a liquid compound.
By using1H-NMR confirmed that the obtained compound was a hydrolyzable organosilane compound 4 containing a lipophilic group represented by the following formula (M).
[ solution 69]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CH2CH2C 2H-Si(-OCH3)3)6H
δ0.7(-(CH2)7CHx-Si-)2H
δ1.1-1.5(-(C 2H)7-，-OCH2C 3H，-C 2HC 2HCH2-Si(-OCH3)3)29H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3(-OOC-C 2H-)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)27H
δ4.1(-OC 2HCH3)2H
δ7.4(-Si-C6 4H-Si-)4H
[ example 5]
75.7g (3.90X 10) of 1, 4-bis (dimethylsilyl) benzene placed in a reaction vessel-1mol) are heated to 80 ℃. Next, a 1.0X 10 toluene solution to which chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 10.0g (7.80X 10) of ethyl 4-pentenoate are added dropwise over a period of 3 hours-2mol), heated and stirred at 80 ℃ for 3 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 23.4g of a compound represented by the following formula (N).
[ solution 70]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2CH2CH2C 2H-Si-)2H
δ1.2(-OCH2C 3H)3H
δ1.3(-(CH2CH2C 2HCH2-Si-)2H
δ1.6(-(CH2C 2HCH2CH2-Si-)2H
δ2.3(-OOC-C 2H-)2H
δ4.1(-OC 2HCH3)2H
δ4.4(-Si-H)1H
δ7.5(-Si-C6 4H-Si-)4H
In a reaction vessel, a catalyst represented by the following formula (B)
[ solution 71]
5.00g (2.38X 10) of the compound shown-2mol), 10.0g of toluene, PF50603.00g, 12.0mg of tris (pentafluorophenyl) borane (2.35X 10)-5mol) at room temperature. Then, a solution of the compound represented by the following formula (N) was slowly dropped
[ chemical formula 72]
The compound represented by (7.66 g) (2.38X 10)-2mol), stirred at 30 ℃ for 1 hour. Then, PF5060 was added, the fluorine layer as the lower layer was removed by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 12.2g of a compound represented by the following formula (O)A compound (I) is provided.
[ solution 73]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)2C 3H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H)3H
δ1.1-1.3(-OOC-CH2CH2C 2HCH2-Si-，-OCH2C 3H，-CH2-(C 3H)5-CH3)15H
δ1.4-1.5(-C 3H-(C 2H)5-CH3)2H
δ1.6(-OOC-CH2C 2HCH2CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-OOC-C 2H-)6H
δ4.1(-OC 2HCH3)2H
δ5.0((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel containing a catalyst represented by the following formula (O)
[ chemical formula 74]
10.0g (1.89X 10) of the compound represented-2mol), 2.00g of toluene, heated to 80 ℃. Next, a methyl of chloroplatinic acid/vinylsiloxane complex was addedBenzene solution 1.0X 10-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 9.22g (7.56X 10) of trimethoxysilane-2mol), aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 12.1g of a liquid compound.
By using1H-NMR confirmed that the obtained compound was a hydrolyzable organosilane compound 5 containing a lipophilic group represented by the following formula (P).
[ solution 75]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CH2CH2C 2H-Si(-OCH3)3)4H
δ0.7(-OOC-CH2CH2CH2C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H)3H
δ1.1-1.5(-OOC-CH2CH2C 2HCH2-Si-，-OCH2C 3H，-C 2H-(C 2H)5-CH3，-C 2HC 2HCH2-Si(-OCH3)3)25H
δ1.6(-OOC-CH2C 2HCH2CH2-Si-)2H
δ2.2-2.3(-OOC-C 2H-)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)18H
δ4.1(-OC 2HCH3)2H
δ7.5(-Si-C6 4H-Si-)4H
[ example 6]
1, 4-bis (dimethylsilyl) benzene placed in a reaction vessel32.8g(1.69×10-1mol) are heated to 80 ℃. Next, a 1.0X 10 toluene solution to which chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 10.0g (3.38X 10) of octyl 10-undecenoate is added dropwise over a period of 3 hours-2mol), heated and stirred at 80 ℃ for 3 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure, whereby 15.2g of a compound represented by the following formula (Q) was obtained.
[ 76]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.9(-OCH2(CH2)6C 3H)3H
δ1.2-1.5(-(C 2H)7-，-OCH2(C 2H)6CH3)26H
δ1.6(-OOC-CH2C 3H(CH2)7CH2-Si-)2H
δ2.3(-OOC-C 2H-)2H
δ4.1(-OC 2H(CH2)6CH3)2H
δ4.4(-Si-H)1H
δ7.5(-Si-C6 4H-Si-)4H
In a reaction vessel, a catalyst represented by the following formula (B)
[ solution 77]
5.00g (2.38X 10) of the compound shown-2mol), 10.0g of toluene, PF50603.00g of tris (pentafluorophenyl) borane12.0mg(2.35×10-5mol) at room temperature. Then, a solution of the compound represented by the following formula (Q) was slowly dropped
[ solution 78]
11.7g (2.38X 10) of the compound shown-2mol), stirred at 30 ℃ for 1 hour. Then, PF5060 was added, the lower fluorine layer was removed by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 16.7g of a compound represented by the following formula (R).
[ solution 79]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H，-(CH2)7C 2H-Si-)6H
δ1.1-1.5(-(C 2H)7-，-CH2-(C 2H)5-CH3，-OCH2(C 2H)6CH3)36H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-OOC-C 3H-)6H
δ4.1(-OC 2H(CH2)6CH3)2H
δ5.0((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel containing a catalyst represented by the following formula (R)
[ solution 80]
10.0g (1.43X 10) of the compound shown-2mol), 2.00g of toluene, heated to 80 ℃. Next, a 1.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 6.99g (5.73X 10) of trimethoxysilane-2mol), and aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 11.5g of a liquid compound.
By using1H-NMR confirmed that the obtained compound was a hydrolyzable organosilane compound 6 containing a lipophilic group represented by the following formula (S).
[ solution 81]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CHaCH2C 2H-Si(-OCH3)3)4H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H，-OCH2(CH2)6C 3H)6H
δ1.1-1.5(-(C 2H)7-，-OCH2(C 2H)6CH3，-C 3H-(C 2H)5-CH3，-C 2HC 2HCH2-Si(-OCH3)3)46H
δ1.6(-OOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3(-OOC-C 2H-)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)18H
δ4.1(-OC 2H(CH2)6CH3)2H
δ7.5(-Si-C6 4H-Si-)4H
[ example 7]
40.6g (2.09X 10) of 1, 4-bis (dimethylsilyl) benzene was placed in a reaction vessel-1mol) are heated to 80 ℃. Next, a 1.0X 10 toluene solution to which chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol) was added dropwise over a period of 3 hours to the solution of the following formula (T)
[ solution 82]
10.0g (4.18X 10) of the compound shown-2mol), heated and stirred at 80 ℃ for 6 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure to obtain 17.1g of a compound represented by the following formula (U).
[ solution 83]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ1.0-1.2(-N(CH2C 3H)2)6H
δ1.2-1.5(-(C 2H)7-)14H
δ1.6(-NOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.3(-NOC-C 2H-)2H
δ3.2-3.4(-N(C 2HCH3)2)4H
δ4.4(-Si-H)1H
δ7.5(-Si-C6 4H-Si-)4H
In a reaction vessel, a catalyst represented by the following formula (B)
[ solution 84]
5.00g (2.38X 10) of the compound shown-2mol), 10.0g of toluene, PF50603.00g, 12.0mg of tris (pentafluorophenyl) borane (2.35X 10)-5mol) at room temperature. Then, the solution was slowly dropped into the reaction vessel represented by the following formula (U)
[ solution 85]
10.3g (2.38X 10) of the compound shown-2mol), stirred at 30 ℃ for 1 hour. Then, PF5060 was added, the lower fluorine layer was removed by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 14.8g of a compound represented by the following formula (V).
[ solution 86]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H)3H
δ1.1-1.3(-(C 2H)7-，-N(CH2C 3H)2，-CH2-(C 2H)5-CH3)30H
δ1.4-1.5(-C 2H-(C 2H)5-CH3)2H
δ1.6(-NOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-NOC-C 2H-)6H
δ3.2-3.4(-N(C 2HCH3)2)4H
δ5.0((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel containing a catalyst represented by the following formula (V)
[ solution 87]
10.0g (1.56X 10) of the compound shown-2mol), 2.00g of toluene, heated to 80 ℃. Next, a 1.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 7.61g (6.24X 10) of trimethoxysilane-2mol), and aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 11.1g of a liquid compound.
By using1H-NMR confirmed that the obtained compound was a hydrolyzable organosilane compound 7 containing a lipophilic group represented by the following formula (W).
[ solution 88]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CH2CH2C 2H-Si(-OCH3)3)4H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H)3H
δ1.1-1.5(-(C 2H)7-，-N(CH2C 3H)2，-C 2H-(C 2H)5-CH3，-C 2HC 2HCH2-Si(-OCH3)3)40H
δ1.6(-NOC-CH2CH 2(CH2)7CH2-Si-)2H
δ2.2-2.3(-NOC-C 2H-)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)18H
δ3.2-3.4(-N(C 2HCH3)2)4H
δ7.5(-Si-C6 4H-Si-)4H
[ example 8]
31.1g (1.60X 10) of 1, 4-bis (dimethylsilyl) benzene placed in a reaction vessel-1mol) are heated to 80 ℃. Next, a 1.0X 10 toluene solution to which chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol) was added dropwise over a period of 3 hours to the solution of the following formula (X)
[ solution 89]
10.0g (3.20X 10) of the compound shown-2mol)，The mixture was heated and stirred at 80 ℃ for 6 hours. Then, the solvent and the unreacted material were distilled off under reduced pressure, whereby 15.2g of a compound represented by the following formula (Y) was obtained.
[ solution 90]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.9(-SCH2(CH2)6C 3H)3H
δ1.2-1.5(-(C 2H)7-，-SCH2(C 2H)6CH3)26H
δ1.6(-SOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.3(-SOC-C 2H-)2H
δ2.8(-SC 2H(CH2)6CH3)2H
δ4.4(-Si-H)1H
δ7.5(-Si-C6 4H-Si-)4H
In a reaction vessel, a catalyst represented by the following formula (B)
[ solution 91]
5.00g (2.38X 10) of the compound shown-2mol), 10.0g of toluene, PF50603.00g, 12.0mg of tris (pentafluorophenyl) borane (2.35X 10)-5mol) at room temperature. Then, a solution of the following formula (Y) was slowly dropped
[ solution 92]
The compound represented by (12.1 g) (2.38X 10)-2m0l) was stirred at 30 ℃ for 1 hour. Then, PF5060 was added, the lower fluorine layer was removed by a liquid separation operation, and the remaining solvent was distilled off under reduced pressure to obtain 16.3g of a compound represented by the following formula (Z).
[ solution 93]
1H-NMR
δ0.2-0.4(-Si-C 3H)12H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H，-SCH2(CH2)6C 3H)6H
δ1.1-1.3(-(C 2H)7-，-SCH2(C 3H)6CH3，-CH2-(C 2H)5-CH3)36H
δ1.4-1.5(-C 2H-(C 3H)5-CH3)2H
δ1.6(-SOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3((-C 2H-CH＝CH2)2，-SOC-C 2H-)6H
δ2.8(-SC 2H(CH2)6CH3)2H
δ5.0((-CH2-CH＝C 2H)2)4H
δ5.8((-CH2-CH＝CH2)2)2H
δ7.5(-Si-C6 4H-Si-)4H
Placing a reaction vessel containing a catalyst represented by the following formula (Z)
[ solution 94]
10.0g (1.40X 10) of the compound shown-2mol), 2.00g of toluene, heated to 80 ℃. Next, a 1.0X 10 toluene solution of chloroplatinic acid/vinylsiloxane complex was added-2g (calculated by Pt simple substance, containing 6.4X 10)-7mol), 6.83g (5.60X 10) of trimethoxysilane-2mol), aging at 80 ℃ for 24 hours. Then, the solvent and unreacted materials were distilled off under reduced pressure to obtain 11.0g of a liquid compound.
By using1H-NMR confirmed that the obtained compound was a hydrolyzable organosilane compound 8 containing a lipophilic group represented by the following formula (A').
[ solution 95]
δ0.2-0.4(-Si-C 3H)12H
δ0.5(-CH2CH2C 2H-Si(-OCH3)3)4H
δ0.7(-(CH2)7C 2H-Si-)2H
δ0.8-0.9(-CH2-(CH2)5-C 3H，-SCH2(C 2H)6CH3)6H
δ1.1-1.5(-(C 2H)7-，-SCH2(C 2H)6CH3，-C 2H-(C 2H)5-CH3，-C 2HCH 2CH2-Si(-OCH3)3)46H
δ1.6(-SOC-CH2C 2H(CH2)7CH2-Si-)2H
δ2.2-2.3(-SOC-C 2H-)2H
δ3.5(-CH2CH2CH2-Si(-OC 3H)3)18H
δ2.8(-SC 2H(CH2)6CH3)2H
δ7.5(-Si-C6 4H-Si-)4H
As comparative examples, the following compounds were used.
Comparative example 1
A lipophilic group-containing hydrolyzable organosilicon compound 9 represented by the following formula (B
[ solution 96]
Comparative example 2
A hydrolyzable organosilane compound 10 represented by the following formula (C')
[ solution 97]
Preparation of surface treatment agent and formation of cured coating film
The lipophilic group-containing hydrolyzable silanes represented by the formulae (D), (G), (J), (M), (P), (S), (W), (a ') obtained in examples 1 to 8 and the lipophilic group-containing hydrolyzable silane compound 9 represented by the formula (B') of comparative example 1 were dissolved in propylene glycol monomethyl ether so that the concentration became 0.1 mass%, and acetic acid was dissolved so that the concentration became 0.1 mass%, thereby preparing a surface treatment agent. Then, Gorilla glass manufactured by Corning corporation was dip-coated and cured at 120 ℃ for 30 minutes to prepare a cured coating film having a thickness of 3 nm.
The surface treatment agent was prepared by dissolving the hydrolyzable organosilane compound 10 represented by the formula (C') of comparative example 2 in Novec 7200 (ethyl perfluorobutyl ether, manufactured by 3M) so that the concentration thereof became 0.1 mass%. Then, Gorilla glass manufactured by Corning corporation was dip-coated and cured at 120 ℃ for 30 minutes to prepare a cured coating film having a thickness of 8 nm.
As comparative example 3 (blank), Gorilla glass manufactured by corning corporation was used which was not coated with anything.
Evaluation of lipophilicity
[ evaluation of lipophilicity ]
The contact angle (lipophilicity) of the cured film with respect to oleic acid was measured using a contact angle meter Drop Master (manufactured by Kyowa interface science Co., Ltd.) for the glass on which the cured film prepared as described above was formed (droplet: 2. mu.l, temperature: 25 ℃ and humidity (RH): 40%). For the measurement, the droplet was attached to the cured coating film, and then the measurement was performed after 40 seconds. The results (oleic acid contact angle) are shown in table 1.
In the early stages, the examples show good lipophilicity.
Evaluation of Water repellency
[ evaluation of Water repellency ]
The contact angle (water repellency) of the glass on which the cured film produced above was formed was measured with respect to water using a contact angle meter Drop Master (manufactured by Kyowa interface science Co., Ltd.) (droplet: 2. mu.l, temperature: 25 ℃ and humidity (RH): 40%). The results (water contact angle) are shown in table 1.
Evaluation of fingerprint Low visibility
[ evaluation of fingerprint visibility ]
The glass on which the cured film prepared above was formed was visually evaluated for functionality by adhering sebum thereto with a load of 1kg and using the following 4 ratings for visibility. The results are shown in table 1.
4: hardly seeing fingerprint
3: see very few fingerprints
2: the fingerprint is shallow, but can be clearly seen
1: the fingerprint can be clearly seen
[ evaluation of haze ]
The glass on which the cured film prepared above was formed was allowed to adhere sebum with a load of 1kg, and the haze was measured using a haze meter NDH5000 (manufactured by japan electrochromism industries).
[ evaluation of refractive index ]
The refractive indices of the organic silane compounds of examples 1 to 8 and comparative examples 1 and 2 were evaluated according to JIS K0062.
[ evaluation of abrasion resistance ]
The glass on which the cured films of examples 1 to 8 and comparative example 1 produced above were formed was evaluated for abrasion resistance by measuring the contact angle (water repellency) with water of the cured film after being rubbed 2000 times under the following conditions using a friction tester (manufactured by new eastern science corporation) in the same manner as described above. The test environment conditions were 25 ℃ and 40% humidity (RH). The results (water contact angle after abrasion) are shown in table 1.
Resistance to wear of rubber
Rubber: manufactured by Minoan Co Ltd
Contact area: 6mm phi
Travel distance (single pass): 30mm
Moving speed: 3600 mm/min
Loading: 1kg/6mm phi
[ Table 1]
In the evaluation of low visibility of fingerprints, no fingerprint was recognized in any of examples 1 to 8 and comparative example 1. On the other hand, fingerprints were clearly seen in comparative example 2 in which a perfluoropolyether compound having no lipophilic group was used. In addition, fingerprints were also clearly seen in comparative example 3 in which no surface treatment agent was applied.
In the measurement of haze using a haze meter, the haze values of the examples are all low, and there is a good correlation with the results of the functional evaluation.
In addition, as for the refractive index of the organic silane compound, the refractive index closer to that of sebum (about 1.5) is effective for low visibility of fingerprints.
In all of examples 1 to 8, the water contact angle was 50 ° or more even after the rubber was worn 2000 times, and the durability was improved. The water contact angle of comparative example 1 showing low visibility of fingerprint was less than 50 °, and as a result, abrasion durability was low.
Claims (13)
1. An organosilane compound represented by the following general formula (1):
[ solution 1]
Wherein A is-C (═ O) OR1、-C(＝O)NR1 2、-C(＝O)SR1and-P (═ O) (OR)1)2Any one of (1), R1The compound is hydrogen atom, alkyl with 1-30 carbon atoms, aryl with 6-30 carbon atoms or aralkyl with 7-30 carbon atoms, Y is independently organic group with 2 valence, R is independently alkyl with 1-4 carbon atoms or phenyl, R' is alkyl with 1-20 carbon atoms, aryl with 6-20 carbon atoms or aralkyl with 7-20 carbon atoms, p is 2 or 3, X is hydroxyl or hydrolytic group independently, and n is an integer of 1-3.
2. The organosilane compound according to claim 1, wherein in the formula (1), Y is an alkylene group having 2 to 30 carbon atoms, and the alkylene group having 2 to 30 carbon atoms may contain a group having 2 valence selected from the group consisting of a silylene group, a silylarylene group, and a linear, branched or cyclic organopolysiloxane residue having 2 to 10 silicon atoms and having 2 valence, and may further contain an arylene group having 6 to 20 carbon atoms.
3. The organosilane compound according to claim 1 or 2, wherein in the formula (1), each X is independently selected from a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxy-substituted alkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen atom, an oximo group, an isocyanate group and an cyanate group.
4. The organosilane compound according to any one of claims 1 to 3, which is represented by the following formula (2):
[ solution 2]
In the formula, R2Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, m is independently an integer of 2 to 20, R' is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, p is 2 or 3, and X is independently a hydroxyl group or a hydrolyzable group.
5. The organosilane compound according to any one of claims 1 to 4, wherein the refractive index is 1.45 or more.
6. A surface treatment agent comprising at least 1 of the organosilane compound according to any one of claims 1 to 5 and/or a partial (hydrolytic) condensate thereof.
7. The surface treatment agent according to claim 6, further comprising a solvent.
8. The surface treating agent according to claim 6 or 7, further comprising a hydrolytic condensation catalyst.
9. The surface treatment agent according to any one of claims 6 to 8, which gives a cured coating film having an oleic acid contact angle of 30 ° or less at 25 ℃ and a relative humidity of 40%.
10. The surface treatment agent according to any one of claims 6 to 9, which gives a cured film having a haze of 10 or less when sebum is adhered to the cured film with a load of 1 kg.
11. The surface treatment agent according to any one of claims 6 to 10, which gives a cured coating film having a water contact angle of 50 ° or more after 2000 times of abrasion with a rubber.
12. An article having a cured coating of the surface treatment agent according to any one of claims 6 to 11 on a surface thereof.
13. A method for adjusting the refractive index of a substrate surface to 1.45 to 1.52 according to JIS K0062, which comprises the step of forming a cured coating of the surface treatment agent according to any one of claims 6 to 11 on the substrate surface.
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| PCT/JP2019/027256 WO2020026729A1 (en) | 2018-07-31 | 2019-07-10 | Organosilane compound containing lipophilic group, surface treatment agent and article |
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| WO2021229624A1 (en) * | 2020-05-11 | 2021-11-18 | 信越化学工業株式会社 | Coating agent composition, surface treatment agent comprising said composition, and article surface-treated with said surface treatment agent |
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| JP2001353808A (en) * | 2000-06-13 | 2001-12-25 | Matsushita Electric Ind Co Ltd | Coating film for preventing soil from becoming conspicuous, manufacturing method therefor, display and touch panel using the coating film, and information therminal using display and touch panel |
| JP2010100819A (en) * | 2008-09-25 | 2010-05-06 | Panasonic Electric Works Co Ltd | Method of inhibiting fingerprint soil, anti-fingerprint coating material composition, and coated article thereof |
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| CN103551076B (en) | 2005-04-01 | 2016-07-06 | 大金工业株式会社 | Surface modifier |
| KR101109831B1 (en) | 2005-04-01 | 2012-02-17 | 다우 코닝 코포레이션 | Surface modifier and its use |
| JP5235026B2 (en) | 2010-09-28 | 2013-07-10 | 信越化学工業株式会社 | Fluorooxyalkylene group-containing polymer composition, surface treatment agent containing the composition, and article surface-treated with the surface treatment agent |
| JP2012157856A (en) | 2011-01-13 | 2012-08-23 | Central Glass Co Ltd | Stainproof article and method for manufacturing this article |
| JP5857942B2 (en) | 2011-11-30 | 2016-02-10 | 信越化学工業株式会社 | Fluorine surface treatment agent for vapor deposition and article vapor-deposited with the surface treatment agent |
| US11352378B2 (en) * | 2017-10-26 | 2022-06-07 | Shin-Etsu Chemical Co., Ltd. | Lipophilic group-containing organosilane compound, surface treatment agent and article |
| CN111630123B (en) * | 2018-01-22 | 2023-02-17 | 信越化学工业株式会社 | Coating agent composition, surface treatment agent comprising the same, and article surface-treated with the surface treatment agent |
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| JP2001353808A (en) * | 2000-06-13 | 2001-12-25 | Matsushita Electric Ind Co Ltd | Coating film for preventing soil from becoming conspicuous, manufacturing method therefor, display and touch panel using the coating film, and information therminal using display and touch panel |
| JP2010100819A (en) * | 2008-09-25 | 2010-05-06 | Panasonic Electric Works Co Ltd | Method of inhibiting fingerprint soil, anti-fingerprint coating material composition, and coated article thereof |
| CN104945610A (en) * | 2014-03-31 | 2015-09-30 | 信越化学工业株式会社 | Fluoropolyether-containing polymer-modified silane, surface treating agent, and article |
| CN108137798A (en) * | 2015-10-09 | 2018-06-08 | 信越化学工业株式会社 | Polymer modification phosphonate derivative containing fluoro alkylidene oxide and the surface conditioning agent containing the derivative and the surface treatment method using the surface conditioning agent |
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