CN114341205B - 具有全氟聚醚基的硅氧烷丙烯酸酯 - Google Patents
具有全氟聚醚基的硅氧烷丙烯酸酯 Download PDFInfo
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- CN114341205B CN114341205B CN201980100038.7A CN201980100038A CN114341205B CN 114341205 B CN114341205 B CN 114341205B CN 201980100038 A CN201980100038 A CN 201980100038A CN 114341205 B CN114341205 B CN 114341205B
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- acrylate
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- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 27
- 229920001296 polysiloxane Polymers 0.000 title claims description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 title description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 64
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 15
- 125000000962 organic group Chemical group 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 35
- 239000008199 coating composition Substances 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910003849 O-Si Inorganic materials 0.000 abstract 1
- 229910003872 O—Si Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 98
- -1 fluoroalkyl acrylates Chemical class 0.000 description 45
- 239000000126 substance Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 238000000034 method Methods 0.000 description 28
- 239000002904 solvent Substances 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 229960001545 hydrotalcite Drugs 0.000 description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 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 7
- 238000007259 addition reaction Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 101150065749 Churc1 gene Proteins 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 102100038239 Protein Churchill Human genes 0.000 description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000006459 hydrosilylation reaction Methods 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 4
- MNMVKGDEKPPREK-UHFFFAOYSA-N trimethyl(prop-2-enoxy)silane Chemical compound C[Si](C)(C)OCC=C MNMVKGDEKPPREK-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 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
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 2
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- 239000007848 Bronsted acid Substances 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XBSVWZGULSYIEG-UHFFFAOYSA-N ethenyl hypofluorite Chemical group FOC=C XBSVWZGULSYIEG-UHFFFAOYSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 2
- 229940104873 methyl perfluorobutyl ether Drugs 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
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- 239000011736 potassium bicarbonate Substances 0.000 description 2
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- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
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- 230000001681 protective effect Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-UHFFFAOYSA-N 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- SKRWRXWNQFQGRU-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane Chemical compound CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SKRWRXWNQFQGRU-UHFFFAOYSA-N 0.000 description 1
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
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Classifications
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- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
-
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Abstract
由下述式(1)表示的含氟硅氧烷丙烯酸酯。[PFPE为2价的全氟聚醚链,X为由下述式(2)表示的基团,{Y1为2价有机基团,R2为氢原子、氟原子、甲基或三氟甲基,G为1价烃基或由下述式(3)表示的基团,X‑Z‑PFPE‑Z‑X(1)‑‑‑‑O‑Si(CH3)2‑Y1‑OR1(3)‑‑‑‑SiR3 3(4)(R1为1价烃基,Y1如上所述。虚线表示键合端(下同)。),Q为氢原子、或由下述式(4)表示的基团,(R3为1价烃基。),e为0~2的整数,f为0~2的整数,g为1~3的整数,e+f+g为3。},Z为规定的2价有机基团。]。
Description
技术领域
本发明涉及可光固化的具有全氟聚醚基的硅氧烷丙烯酸酯(以下称为“含氟硅氧烷丙烯酸酯”。)。
背景技术
目前为止,作为可采用紫外线等的光照射而固化的氟化合物,众所周知具有全氟烷基的聚合性单体、包含丙烯酸含氟烷基酯、甲基丙烯酸含氟烷基酯的聚合物。作为代表性的氟化合物,由下述结构式表示的化合物为了对基材表面赋予低反射性、拒水拒油性、防污性、耐磨损性、耐擦伤性等而广泛地使用。
[化1]
但是,近年来,由于担心环境负担,限制应用含有碳原子数8以上的长链全氟烷基的化合物的动向在增强。但是,已知含有碳原子数不到8的全氟烷基的丙烯酸系化合物与具有碳原子数8以上的长链全氟烷基的丙烯酸系化合物相比,其表面特性显著地差(非专利文献1)。
另一方面,已知引入了连续的由碳原子数为3以下的全氟亚烷基和醚键性氧原子组成的全氟聚醚类的可光固化的氟化合物。例如,提出了由六氟氧化丙烯低聚物衍生的含氟丙烯酸系化合物(专利文献1)、由含有氟的聚醚二醇和甲基丙烯酸2-异氰酸酯基乙酯的反应产物构成的氨基甲酸酯丙烯酸酯(专利文献2)。但是,由于含氟化合物的拒水拒油特性,因此与光聚合引发剂、非氟化丙烯酸酯和非氟化有机溶剂的相容性低,可配混的成分及用途有限。
对此,提出了具备环状硅氧烷结构和氨基甲酸酯结构、与非氟系溶剂的相容性优异的含氟丙烯酸酯化合物(专利文献3)。但是,鉴于将该化合物在用于形成减反射膜的组合物中配混,优选具有更低折射率的含氟丙烯酸酯。与非氟系溶剂的相容性与折射率存在折衷的关系,对于为了提高相容性而大量地将氨基甲酸酯结构引入结构中的、专利文献3中所示的含氟丙烯酸酯而言,所形成的被膜的折射率高,损害被膜的低反射性。进而,含氟丙烯酸酯中的丙烯酰基量与折射率也存在折衷的关系,如果为了降低含氟丙烯酸酯的折射率而减少丙烯酰基的含量,则损害所形成的被膜的强度。
由于上述的背景,希望有如下的含氟丙烯酸酯化合物,其满足不会损害与非氟系溶剂的相容性、并且在没有减少丙烯酰基的情况下实现了更低的折射率。
现有技术文献
专利文献
专利文献1:日本特开平5-194322号公报
专利文献2:日本特开平11-349651号公报
专利文献3:日本专利第4873666号公报
非专利文献
非专利文献1:高分子论文集Vol.64,No.4,第181-190页(2007年4月)
发明内容
发明要解决的课题
本发明鉴于上述实际情况而完成,目的在于提供保持丙烯酰基的含量、同时实现了与非氟系溶剂的良好的相容性和低折射率的、具有全氟聚醚基的含氟硅氧烷丙烯酸酯。
用于解决课题的手段
本发明人为了解决上述课题而深入研究,结果发现:下述含氟硅氧烷丙烯酸酯保持丙烯酰基的含量,同时能够实现与非氟系溶剂的良好的相容性和低折射率,完成了本发明。
即,本发明提供:
1.由下述式(1)表示的含氟硅氧烷丙烯酸酯,
[化2]
X-Z-PFPE-Z-X (1)
[式中,PFPE表示数均分子量500~30,000的2价的全氟聚醚链,X各自独立地为由下述式(2)表示的基团,
[化3]
{式(2)中,Y1各自独立地为可包含醚键、可具有环状结构或分支结构的2价的有机基团,R2各自独立地为氢原子、氟原子、甲基、或三氟甲基,G各自独立地为碳原子数1~12的烷基或由下述式(3)表示的基团,
[化4]
(式(3)中,R1为碳原子数1~12的1价烃基,Y1如上所述。虚线表示键合端。)
Q为氢原子、或由下述式(4)表示的基团,
[化5]
(式(4)中,R3各自独立地为碳原子数1~12的1价烃基。虚线表示键合端。)
e为0~2的整数,f为0~2的整数,g为1~3的整数,e+f+g为3。虚线表示键合端。}
Z各自独立地为由下述式表示的2价的有机基团。
[化6]
(式中,虚线表示键合端,**标记表示与所述PFPE的键合部位。)]
2.根据1所述的含氟硅氧烷丙烯酸酯,其中,PFPE为由下述式表示的数均分子量1,000~5,000的全氟聚醚链,
[化7]
(式中,a为a≥1的数,b为b≥1的数,a/b为1/10~10/1的数。带有a及b的括弧内的重复单元的排列可以是任意的。虚线表示键合端。)
3.根据1或2所述的含氟硅氧烷丙烯酸酯,其中,Z为由下述式表示的2价的有机基团,
[化8]
(式中,虚线表示键合端,**标记表示与所述PFPE的键合部位。)
4.根据1~3中任一项所述的含氟硅氧烷丙烯酸酯,其中,Y1为由下述式表示的2价的有机基团,
[化9]
*---CH2CH2---
*---CH2CH2CH2---
*---CH(CH3)CH2---
*---CH2CH2CH(CH3)CH2-----
*---CH2CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2---
(式中,虚线表示键合端,星号(*)表示与硅原子的键合部位。)
5.根据1~4中任一项所述的含氟硅氧烷丙烯酸酯,其中,G为碳原子数1~6的烷基或由上述式(3)表示的基团,式(3)中的R1为甲基、乙基或正丙基,e为1或2,
6.根据5所述的含氟硅氧烷丙烯酸酯,其中,G为碳原子数1~3的烷基,
7.根据1~4中任一项所述的含氟硅氧烷丙烯酸酯,其中,e为0,
8.涂布组合物,其包含根据1~7中任一项所述的含氟硅氧烷丙烯酸酯,
9.根据8所述的涂布组合物,其还包含根据1~7中任一项所述的含氟硅氧烷丙烯酸酯以外的丙烯酸酯或氨基甲酸酯丙烯酸酯,
10.物品,其具有包括根据8或9所述的涂布组合物的固化物的被膜。
发明的效果
本发明的含氟硅氧烷丙烯酸酯在具有与以往的含氟丙烯酸酯同等的丙烯酰基量的同时,兼具与非氟系有机化合物的相容性和低折射率,能够用光固化而形成拒水拒油性的固化物,可用作减反射膜用的树脂或者硬涂层用的添加剂。
具体实施方式
以下对本发明具体地说明。
[含氟硅氧烷丙烯酸酯]
本发明的含氟硅氧烷丙烯酸酯由下述式(1)表示。
[化10]
X-Z-PFPE-Z-X (1)
式(1)中,PFPE为数均分子量500~30,000的2价的全氟聚醚链。优选具有数均分子量优选为1,000~5,000、由下述结构式(5)表示的全氟亚烷基与氧原子交替地连接的结构。再有,本发明中,数均分子量为采用凝胶渗透色谱(GPC)得到的标准聚苯乙烯换算值。
[化11]
式(5)中,A表示碳原子数1~3的全氟亚烷基,可相同也可不同,排列可为任意。n为1以上的数,优选6~60的数,更优选10~35的数。虚线表示键合端(下同)。
作为由A表示的碳原子数1~3的全氟亚烷基的具体例,可列举出下述所示的结构。
[化12]
在全氟聚醚链中,从成为显现滑动性的弯曲点的氧原子大量存在的方面、不存在阻碍链的弯曲运动的分支结构的方面等出发,作为A,优选全氟亚甲基及全氟亚乙基。
就由PFPE表示的2价的全氟聚醚链而言,如果考虑工业上容易获得的方面,特别优选氧二氟亚甲基与氧四氟亚乙基共存的由下述式(6)表示的全氟聚醚链。
[化13]
---CF2(OCF2)a(OCF2CF2)bOCF2--- (6)
在式(6)中,全氟氧亚甲基的数(a)为a≥1的数,全氟氧亚乙基的数(b)为b≥1的数。对全氟氧亚甲基的数(a)与全氟氧亚乙基的数(b)之比(a/b)并无特别限定,优选1/10~10/1的数,更优选3/10~10/3的数。带有a及b的括弧内的重复单元的排列可为任意。
X各自独立地为由下述式(2)表示的基团。
[化14]
R2各自独立地为氢原子、氟原子、甲基、或三氟甲基,优选氢原子、甲基,特别优选氢原子。
Y1各自独立地为可包含醚键(不过,不包括在与氧原子的键合末端包含O而产生-O-O-键的基团)、可具有环状结构或分支结构的2价的有机基团。作为Y1,例如可列举出碳原子数2~20、优选2~10的亚烷基等,优选由以下的结构式表示的基团。
[化15]
*---CH2CH2---
*---CH2CH2CH2---
*---CH(CH3)CH2---
*---CH2CH2CH(CH3)CH2-----
*---CH2CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CH2CH2---
*---CH2CHzCHz-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CHzCH2-O-CH2CH2---
(式中,星号(*)表示与硅原子的键合部位(下同)。)
Y1特别优选为由以下的结构式表示的2价的有机基团。
[化16]
*---CH2CH2---
*---CH2CH2CH2---
*---CH2CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2---
G各自独立地为碳原子数1~12的烷基或由下述式(3)表示的基团。
[化17]
作为G的烷基,例如可列举出甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、正己基、环己基等。G为优选碳原子数1~6、更优选碳原子数1~4、进一步优选碳原子数1~3的烷基,特别优选甲基、乙基、正丙基。
式(3)中,R1为碳原子数1~12的1价烃基,具体地,例如可列举出甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、正己基、环己基等烷基、苯基等芳基等。作为R1,优选碳原子数1~3的烷基,更优选甲基、乙基、正丙基。
Q为氢原子、或由下述式(4)表示的基团。
[化18]
R3各自独立地为碳原子数1~12的1价烃基,具体地,可列举出与对于R1例示的基团相同的基团。作为R3,优选碳原子数1~3的烷基,更优选甲基、乙基、正丙基。
e为0~2的整数,优选为0,f为0~2的整数,g为1~3的整数,e+f+g为3。
Z各自独立地为由下述式表示的2价的有机基团。
[化19]
(式中,**标记表示与PFPE的键合部位(下同)。)
这些中,优选由下述式表示的基团。
[化20]
这些中,特别优选由下述式表示的基团。
[化21]
[制造方法]
本发明的含氟硅氧烷丙烯酸酯例如能够采用以下的方法制造。
[1]氢硅氧烷的合成
首先,通过使由下述式(7)表示的在两末端具有烷氧基甲硅烷基的全氟聚醚与由下述式(8a)和/或(8b)表示的具有Si-H键的化合物进行共水解缩合,从而能够制造由下述式(9)表示的具有全氟聚醚基的氢硅氧烷。
[化22]
式中,R4、R5各自独立地为碳原子数1~12、优选1~6、更优选1~4的烷基,R6为碳原子数1~12、优选1~6、更优选1~4的烷基。w各自独立地为0~2的整数,PFPE及Z如上所述(下同)。
作为R4、R5、R6,例如可列举出甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、正戊基、正己基、环己基等烷基,优选为甲基、乙基、正丙基、正丁基。
作为得到的多官能氢硅氧烷的具体例,可列举出由下述式表示的实例等,但并不限定于这些。
[化23]
在共水解中,就化合物(8a)和/或(8b)相对于化合物(7)的配混量而言,为了防止化合物(7)之间的交联,相对于化合物(7)的烷氧基1当量,以硅换算计,使用2当量以上的化合物(8a)和/或(8b),进行了共水解后,优选采用减压馏除将未反应的化合物(8a)和/或(8b)除去,相对于化合物(7)的烷氧基1当量,以硅换算计,优选在2~10当量、特别是2~6当量的存在下使化合物(8a)和/或(8b)反应。再有,在将化合物(8a)和化合物(8b)并用时,化合物(8a)和化合物(8b)的添加量(质量比)优选(8a)/(8b)=50/1~1/50的比例。
在实施共水解时,优选使用水解催化剂。作为使用的水解催化剂,能够使用以往公知的催化剂,例如可列举出盐酸、硝酸、硫酸、卤化氢、羧酸、磺酸等酸;酸性或弱酸性的无机盐;离子交换树脂等固体酸;氨、氢氧化钠等无机碱类;三丁胺、1,5-二氮杂双环[4.3.0]壬烯-5(DBN)、1,8-二氮杂双环[5.4.0]十一碳烯-7(DBU)等有机碱类;有机锡化合物,有机钛化合物、有机锆化合物、有机铝化合物等有机金属化合物等,这些可单独使用1种,也可将2种以上的多种并用。
本发明中,特别优选选自盐酸、硝酸、硫酸、甲磺酸等酸;有机锡化合物、有机钛化合物及有机铝系化合物中的有机金属化合物。作为有机金属化合物,具体地,可列举出二月桂酸二丁基锡、二辛酸二丁基锡、二乙酸二丁基锡、二月桂酸二辛基锡、二辛酸二辛基锡、二乙酸二辛基锡、双乙酰乙酸二丁基锡、双乙酰月桂酸二辛基锡、钛酸四丁酯、钛酸四壬酯、四甘醇甲基醚钛酸酯、四甘醇乙基醚钛酸酯、双(乙酰丙酮基)二丙基钛酸酯、乙酰丙酮铝、双(乙酰乙酸乙酯)单正丁酸铝、乙酰乙酸乙酯二正丁酸铝、三(乙酰乙酸乙酯)铝、它们的水解物等。这些中,从反应性的观点出发,优选盐酸、硝酸、甲磺酸等酸;钛酸四丁酯、乙酰乙酸乙酯二正丁酸铝、双(乙酰乙酸乙酯)单正丁酸铝及它们的水解物,特别优选甲磺酸。
对水解催化剂的量并无特别限定,相对于式(7)的化合物的硅原子上的烷氧基1摩尔,优选0.001~15摩尔%,特别优选0.001~10摩尔%。
上述共水解·缩合反应可在有机溶剂的存在下进行。作为有机溶剂,只要与上述的各原料化合物相容,则并无特别限制,作为其具体例,可列举出甲苯、二甲苯等芳族烃类;己烷、辛烷等烃类;甲乙酮、甲基异丁基酮等酮类;醋酸乙酯、醋酸异丁酯等酯类;甲醇、乙醇、异丙醇、丁醇、异丁醇、叔丁醇等醇类;氟系溶剂等。
作为氟系溶剂,例如可列举出1,3-双(三氟甲基)苯、三氟甲苯等含氟芳族烃类;全氟己烷、全氟甲基环己烷等碳原子数3~12的全氟碳类;1,1,2,2,3,3,4-七氟环戊烷、1,1,1,2,2,3,3,4,4,5,5,6,6-十三氟辛烷等氢氟烃类;C3F7OCH3、C4F9OCH3、C4F9OC2H5、C2F5CF(OCH3)C3F7等氢氟醚类;Fomblin、Galden(索尔维制造)、Demnum(大金工业(株)制造)、Krytox(科慕制造)等聚(全氟亚烷基醚)类等。
在上述反应中,优选添加水。就水解时使用的水的添加量而言,优选为了使原料的烷氧基的全部水解所需的量的1倍量~5倍量,特别优选1.5倍量~3倍量。
反应条件通常优选-5~20℃下15~300分钟,更优选0~10℃下30~180分钟。
[2]氢化硅烷化反应
其次,对于氢硅氧烷(9),使由下述式(10a)表示的烯烃化合物和根据需要使用的由式(10b)表示的烯烃化合物进行氢化硅烷化加成反应。
[化24]
R7-Y2-O-Q (10a)
R7-Y2-O-R1 (10b)
R7为可与Si-H基加成反应的烯烃基,优选碳原子数2~8的烯基,例如可列举出乙烯基、烯丙基、1-丙烯基、异丙烯基、1-丁烯基、异丁烯基等。这些中,优选乙烯基、烯丙基。Y2为单键、或可包含醚键的2价的有机基团(不过,不包括在与氧原子的键合末端包含0而产生-0-0-键的基团),可具有环状结构、分支结构。作为Y2的2价的有机基团,可列举出碳原子数1~18、优选1~8的亚烷基等,具体地,例如可列举出由下述结构式表示的基团。Q和R1如上所述。
[化25]
·---CH2---
·---CH(CH3)CH2---
·---CH2-O-CH2CH2---
·---CH2-O-CH2CH2O-CH2CH2---
·---CH2-O-CH2CH2O-CH2CH2-O-CH2CH2---
·---CH2-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CH2CH2---
·---CH2-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2----
(式中,·标记表示与R7的键合部位(下同)。)
Y2特别优选为单键及由以下的结构式表示的2价的有机基团。
[化26]
·---CH2---
·---CH2-O-CH2CH2---
·---CH2-O-CH2CH2O-CH2CH2---
作为由式(10a)表示的化合物的具体例,例如可列举出下述的实例等。
[化27]
CH2=CHCH2OSi(CH3)3
CH2=CHCH2OCH2CH2OH
化合物(10a)的添加量相对于1当量的氢硅氧烷(9)的氢甲硅烷基,优选0.2~5当量,更优选为0.5~3当量。
另外,作为由式(10b)表示的化合物的具体例,例如可列举出下述的实例等。
[化28]
CH2-CHCH2OCH3
CH2=CHCH2OCH2CH2OCH3
CH2=CHCH2OCH2CH2OCH2CH2OCH3
CH2=CHCH2OCH2CH2OCH2CH2OCH2CH2OCH3
CH2=CHCH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2OCH3
在使用化合物(10b)的情况下,其添加量相对于1当量的氢硅氧烷(9)的氢甲硅烷基,优选0.1~0.8当量,更优选为0.1~0.5当量。
在将化合物(10a)及化合物(10b)并用时,化合物(10a)与化合物(10b)的添加量(质量比)优选为(10a)/(10b)=50/1~0.5/1的比例。
加成反应即使不使用溶剂也可实施,根据需要可用溶剂稀释。优选地,此时的稀释溶剂不阻碍氢化硅烷化、使反应后生成的下述化合物(11)可溶,优选为在目标的反应温度下将化合物(9)、化合物(10a)、和根据需要使用的化合物(10b)溶解的稀释溶剂。具体地,例如优选苯、甲苯、二甲苯等芳族烃系溶剂;六氟间二甲苯、次苄基三氟等氟改性芳族烃系溶剂;甲基全氟丁基醚、全氟(2-丁基四氢呋喃等氟改性醚系溶剂等,在这些中,优选甲苯、二甲苯、六氟间二甲苯。
优选将催化剂用于氢化硅烷化反应。催化剂能够使用例如包含铂、铑、钯等铂族金属的化合物。这些中,优选包含铂的化合物,例如能够使用六氯铂(IV)酸六水合物、铂羰基乙烯基甲基络合物、铂-二乙烯基四甲基二硅氧烷络合物、铂-环乙烯基甲基硅氧烷络合物、铂-辛醛/辛醇络合物、氯铂酸与烯烃、醛、乙烯基硅氧烷或炔属醇类等的络合物、负载于活性炭的铂等。就催化剂的配混量而言,相对于反应体系整体的质量,优选所含的铂族金属量成为0.1~5,000ppm的范围,更优选为1~1,000ppm。
在加成反应中,对将各成分混合的顺序并无特别限制,例如能够采取将包含化合物(9)、化合物(10a)和根据需要使用的化合物(10b)和催化剂的混合物从室温慢慢地加热到加成反应温度的方法;将包含化合物(9)、化合物(10a)与根据需要使用的化合物(10b)和稀释溶剂的混合物加热到目标的反应温度后添加催化剂的方法;在加热到目标的反应温度的包含化合物(10a)、根据需要使用的化合物(10b)和催化剂的混合物中滴入化合物(9)的方法;在加热到目标的反应温度的化合物(9)中滴入包含化合物(10a)、根据需要使用的化合物(10b)和催化剂的混合物的方法等。这些中,特别优选将包含化合物(9)、化合物(10a)与根据需要使用的化合物(10b)和稀释溶剂的混合物加热到目标的反应温度后添加催化剂的方法、或者、在加热到目标的反应温度的化合物(9)中滴入包含化合物(10a)、根据需要使用的化合物(10b)和催化剂的混合物的方法。就这些方法而言,能够将各成分或混合物根据需要用溶剂稀释而使用。
在使化合物(10a)及(10b)与化合物(9)加成反应的情况下,优选地,在进行了化合物(9)和化合物(10b)的加成反应后,使用过剩量的化合物(10a)进行加成反应,将未反应的化合物(10a)除去精制。此时,在化合物(10a)及化合物(10b)中,可将R7、Y2、R1、Q彼此不同的化合物混合使用。
加成反应优选通常在20~120℃下进行30~300分钟,更优选在50~100℃下进行30~120分钟。
采用上述的方法,得到由下述式(11)表示的化合物。
[化29]
X0-Z-PFPE-Z-X0 (11)
式(11)中,X0各自独立地为下述的基团。
[化30]
/>
Q、Y1、R1、R5、w如上所述,h为1~3的整数,i为0~2的整数,h+i+w=3。再有,式(2)中,对应于e=w+i、f=h-g。
[3]脱保护反应
在Q为由式(4)表示的甲硅烷基的情况下,通过将其一部分或全部脱保护以转变为氢原子,从而构筑将随后与包含(甲基)丙烯酰基的酰氯化合物发生反应的反应点。应予说明,本发明中,(甲基)丙烯酰基表示丙烯酰基或甲基丙烯酰基。
脱保护的条件能够采用以往公知的手法,并无特别限定,能够列举出采用氟离子的方法、采用酸(布朗斯台德酸、路易斯酸)的方法、采用碱(布朗斯台德碱、路易斯碱)的方法、在中性条件下使过剩的醇发挥作用的方法、采用N-溴琥珀酰亚胺、氢化二异丁基铝、钯络合物等的方法等。这些中,优选采用酸(布朗斯台德酸、路易斯酸)的方法、在中性条件下使过剩的醇发挥作用的方法,特别优选在中性条件下使过剩的醇发挥作用的方法。此时,作为发挥作用的醇,优选甲醇、乙醇、丙醇、丁醇、戊醇等,特别优选甲醇、乙醇。就醇的添加量而言,相对于1当量的式(4)的甲硅烷基,优选1~50当量。反应条件优选通常在50~100℃下进行60~1,440分钟。
[4]酯化反应
通过使将上述式(11)中的甲硅烷基脱保护的化合物(11’)中所含的羟基的一部分或全部、或化合物(11)的Q为氢原子的情况下使(化合物(11”))的羟基的一部分或全部与由下述式(12)表示的(甲基)丙烯酰氯反应,形成酯键,从而能够得到由式(1)表示的本发明的含氟硅氧烷丙烯酸酯。
(式中,R2如上所述。)
就化合物(11’)或(11”)与化合物(12)的反应而言,为了将副产的盐酸中和,在碱的存在下、在0~100℃、优选0~80℃的条件下将两者混合30~180分钟而进行。
对碱的种类并无特别限定,例如可列举出氨、三甲胺、三乙胺、二异丙胺、三丙胺、N,N-二异丙基乙基胺、三丁胺、吡啶、N,N-二甲基氨基吡啶、1,5-二氮杂双环[4.3.0]壬烯-5(DBN)、1,8-二氮杂双环[5.4.0]十一碳烯-7(DBU)等胺化合物;碳酸氢钠、碳酸氢钾、碳酸氢锂、碳酸钠、碳酸钾、碳酸锂、氢氧化钠、氢氧化锂、氢氧化钾等无机碱;它们的水溶液等。这些并不限定于其1种,也可作为2种或其以上的混合物使用。这些中,优选三乙胺、吡啶、碳酸氢钠、碳酸氢钾、氢氧化钠、氢氧化钾,特别优选三乙胺。
就化合物(12)相对于化合物(11’)或(11”)的配混量而言,相对于化合物(11’)或(11”)具有的羟基,优选1~10当量,更优选1~5当量,特别优选1~3当量。
就碱相对于化合物(12)的配混量而言,相对于由化合物(12)产生的盐酸,优选1~10当量,更优选1~5当量,特别优选1~3当量。
在上述酯化反应中,对各成分的混合顺序并无特别限制,例如,能够采取将包含化合物(11’)或(11”)、化合物(12)和碱的混合物从室温慢慢地加热到酯化反应温度的方法、将包含化合物(11’)或(11”)和化合物(12)的混合物加热到目标的反应温度后加入碱的方法、将包含化合物(11’)或(11”)和碱的混合物加热到目标的反应温度后加入化合物(12)的方法、将包含化合物(12)和碱的混合物加热到目标的反应温度后加入化合物(11’)或(11”)的方法、将化合物(12)加热到目标的温度后滴入包含化合物(11’)或(11”)和碱的混合物的方法等。这些中,特别优选将包含化合物(11’)或(11”)和碱的混合物加热到目标的反应温度后滴入化合物(12)的方法。
在这些方法中,能够将各成分或混合物根据需要用溶剂稀释而使用。作为用于稀释的溶剂,只要是不与羟基及酰氯反应的溶剂,则能够无特别限制地使用,具体地,优选芳族烃系溶剂(苯、甲苯、二甲苯);氟改性芳族烃系溶剂(六氟间二甲苯、次苄基三氟等);氟改性醚系溶剂(甲基全氟丁基醚、全氟(2-丁基四氢呋喃)等);酮系溶剂(丙酮、甲乙酮、甲基异丁基酮、环戊酮、环己酮等);醚系溶剂(四氢呋喃、***、二异丙基醚、二丁基醚等)等。这些中,优选丙酮、甲乙酮、甲基异丁基酮、六氟间二甲苯。
这样合成的含氟硅氧烷丙烯酸酯成为经由酯键具有丙烯酰基的结构。由此,从结构中减少使折射率上升的氨基甲酸酯键的量,其结果,在没有使丙烯酰基量减少的情况下能降低折射率。
[涂布组合物]
通过将本发明的含氟硅氧烷丙烯酸酯添加到涂布组合物中,从而能够对被膜表面赋予防污性、耐指纹性、拒水性、拒油性。例如,在添加到硬涂层组合物中的情况下,含氟硅氧烷丙烯酸酯相对于硬涂层组合物的基础聚合物100质量份的配混量优选为0.01~20质量份,更优选为0.05~10质量份。如果为这样的范围,能够在不损害硬涂层被膜的硬度的情况下充分地覆盖表面。
另外,本发明的含氟硅氧烷丙烯酸酯能够应用于减反射涂布组合物。这种情况下,含氟硅氧烷丙烯酸酯相对于涂布组合物的基础聚合物100质量份的配混量优选为20~500质量份,更优选为20~300质量份。只要为这样的范围,就能够提供在保持被膜的强度的同时具有低折射率的减反射膜。
在上述涂布组合物中,只要可与本发明的含氟硅氧烷丙烯酸酯混合、固化,能够将本发明的含氟硅氧烷丙烯酸酯以外的丙烯酸酯或氨基甲酸酯丙烯酸酯并用。
作为丙烯酸酯,可列举出包含1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、异氰脲酸环氧乙烷改性二(甲基)丙烯酸酯、异氰脲酸环氧乙烷改性三(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、磷酸三(甲基)丙烯酰氧基乙酯、邻苯二甲酸氢-(2,2,2-三-(甲基)丙烯酰氧基甲基)乙酯、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二(三羟甲基丙烷)四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、山梨醇六(甲基)丙烯酸酯等2~6官能的(甲基)丙烯酸酯化合物、这些(甲基)丙烯酸酯化合物的环氧乙烷、环氧丙烷、表氯醇、脂肪酸、烷基、氨基甲酸酯改性品、使环氧树脂与丙烯酸加成而得到的环氧丙烯酸酯类、在丙烯酸酯共聚物的侧链引入了(甲基)丙烯酰基的共聚物等。
作为氨基甲酸酯丙烯酸酯,可列举包含使多异氰酸酯与具有羟基的(甲基)丙烯酸酯反应而得到的产物、使多异氰酸酯和末端二醇的聚酯与具有羟基的(甲基)丙烯酸酯反应而得到的产物、使多元醇与过剩的二异氰酸酯反应而得到的多异氰酸酯与具有羟基的(甲基)丙烯酸酯反应而得到的产物等。这些中,优选包含使选自(甲基)丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基-3-丙烯酰氧基丙酯和季戊四醇三丙烯酸酯中的具有羟基的(甲基)丙烯酸酯与选自六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、甲苯二异氰酸酯和二苯基甲烷二异氰酸酯中的多异氰酸酯反应而成的氨基甲酸酯丙烯酸酯类。
作为包含这样的丙烯酸酯或氨基甲酸酯丙烯酸酯的涂布组合物,可使用市售品,例如可列举出“ビームセット(Beamset)”荒川化学工业(株)制造、“ユービック(Ubic)”大桥化学工业(株)制造、“UV COAT”オリジン电气(株)(Origin Co.,Ltd.)制造、“カシューUV(Cashew UV)”カシュー(株)(Cashew Co.,Ltd)制造、“デソライト(DeSolite)”JSR(株)制造、“セイカビーム(Seikabeam)”大日精化工业(株)制造、“紫光”日本合成化学(株)制造、“フジハード(Fujihard)”藤仓化成(株)制造、“ダイヤビーム(Diabeam)”三菱人造丝(株)制造、“ウルトラバイン(Ultra-vin)”武藏涂料(株)制造等。
再有,在本发明的涂布组合物中,在不妨碍本发明的效果的范围内能够添加任意的添加剂。作为添加剂的具体例,可列举出非反应性硅油、反应性硅油、非反应性二氧化硅微粒、反应性二氧化硅微粒、非反应性中空二氧化硅微粒、反应性中空二氧化硅微粒等二氧化硅微粒、硅烷偶联剂等密合性赋予剂、防老剂、防锈剂、着色剂、表面活性剂、流变性调整剂、紫外线吸收剂、红外线吸收剂、荧光剂、研磨剂、香料、填充剂、填料、染料和颜料、流平剂、反应性稀释剂、非反应性高分子树脂、抗氧化剂、紫外线吸收剂、光稳定剂、消泡剂、分散剂、抗静电剂、触变性赋予剂等。
通过将本发明的含氟硅氧烷丙烯酸酯在涂布组合物中配混,从而可用于对被膜表面赋予防污、拒水·拒油性、耐指纹性、低反射性。由此,形成被膜,其难以被指纹、皮脂、汗等人脂、化妆品等污染,即使在污垢附着的情况下擦除性也优异,抑制光的映入。因此,本发明的化合物可用作固化性组合物的添加剂,其被施用在有可能人体接触而被人脂、化妆品等污染的物品的表面,和被用于形成涂装膜或保护膜。
作为这样的物品,例如可列举出以光磁盘、CD、LD、DVD、蓝光盘等光盘、全息记录等为代表的光记录介质;眼镜镜片、棱镜、透镜片、表膜、偏振片、光学滤波器、双凸透镜、菲涅尔透镜、减反射膜、光纤、光耦合器等光学部件·光器件;CRT、液晶显示器、等离子体显示器、电致发光显示器、背投型显示器、荧光显示管(VFD)、场致发射投影显示器、调色剂系显示器等各种画面显示设备,特别是PC、移动电话、便携信息终端、游戏机、数码相机、数码摄像机、自动现金取出存入装置、现金自动支付机、自动售货机、汽车用等的导航装置、安全***终端等的图像显示装置、以及也进行其操作的触摸面板(触摸传感器、触摸屏)式图像显示输入装置;移动电话、便携信息终端、便携音乐播放器、便携游戏机、遥控器、控制器、键盘等、车载装置用面板开关等输出装置;移动电话、便携信息终端、照相机、便携音乐播放器、便携游戏机等的壳体表面;汽车的外装、钢琴、高级家具、大理石等的涂装及表面;美术品展示用保护玻璃、橱窗、展示柜、广告用封面、照片架用的封面、手表、汽车用前挡风玻璃、列车、航空器等的窗玻璃、汽车前照灯、尾灯等透明的玻璃制或透明的塑料制(亚克力、聚碳酸酯等)构件、各种反射镜构件等。
另外,将本发明的含氟硅氧烷丙烯酸酯添加在紫外线固化型抗蚀剂液中、进行曝光,从而可对固化后的抗蚀剂表面与将抗蚀剂除去的部分的拒液性赋予大的差异,能够防止显影液、液晶溶液在抗蚀剂树脂表面残存、污染。
实施例
以下示出实施例及比较例,对本发明具体地说明,但本发明并不受下述的实施例限制。再有,1H-NMR测定使用ULTRA SHIELD 400Plus(Bruker公司制造)进行。再有,在下述例中,Me表示甲基。
[实施例1-1]
在干燥氮气氛下在具备回流装置和搅拌装置的5,000mL三口烧瓶中加入由下述式(13)表示的化合物1,255g、四甲基二硅氧烷665g、甲乙酮1,255g、甲磺酸20g,边搅拌边冷却到5℃。向其中滴入离子交换水71g,在将内部温度维持在0~10℃的状态下继续搅拌3小时。然后,加入水滑石(KYOWARD 500SH、协和化学工业(株)制造)100g,在将内部温度维持在0~10℃的状态下进行搅拌2小时,将溶剂、过剩的四甲基二硅氧烷减压馏除后,过滤分离水滑石,得到了由下述式(14)表示的无色透明的液体1,130g。
[化32]
(式中,a1≥1、b1≥1、a1/b1=0.76,带有a1及b1的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
在干燥氮气氛下,对于化合物(14)190g,将烯丙氧基三甲基硅烷117g、甲苯229g、及氯铂酸/乙烯基硅氧烷络合物的甲苯溶液4.3g(以Pt单质计,含有8.3×10-5摩尔)混合,在80℃下搅拌2小时。通过1H-NMR测定及FT-IR测定确认了来自Si-H基的信号消失后,将溶剂和过剩的烯丙氧基三甲基硅烷减压馏除,进行了活性炭处理后,进行过滤,从而得到了由下述式(15)表示的淡黄色透明的液体230g。
[化33]
(式中,a1≥1、b1≥1、a1/b1=0.76,带有a1及b1的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
在干燥氮气氛下,对于化合物(15)230g,加入甲醇2,300g,在67℃下加热搅拌12小时,将副产的三甲基甲氧基硅烷常压馏除后,将过剩的甲醇和三甲基硅烷减压馏除,得到了由下述式(16)表示的淡黄色透明的液体197g。
[化34]
(式中,a1≥1、b1≥1、a1/b1=0.76,带有a1及b1的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
在干燥氮气氛下,对于化合物(16)101g,加入三乙胺41g、六氟间二甲苯505g,边搅拌边升温到60℃。边将内部温度维持在55~60℃,边向其中滴入将丙烯酰氯25g用甲苯50g稀释的混合物,继续搅拌30分钟。其次,在将内部温度维持在55~60℃的状态下滴入乙醇5.8g,继续搅拌1小时。将析出的盐过滤分离,在得到的滤液中加入水滑石(KYOWARD500SH、协和化学工业(株)制造)5.6g和硅酸铝(KYOWARD 700、协和化学工业(株)制造)5.6g,搅拌2小时后,减压馏除,通过将水滑石和硅酸铝过滤分离,从而得到了淡黄色透明的液体56g。
通过1H-NMR测定确认了得到的生成物为由下述式(17)表示的含氟硅氧烷丙烯酸酯。将1H-NMR波谱的化学位移示于表1中。
[化35]
(式中,a1≥1、b1≥1、a1/b1=0.76,带有a1及b1的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
[表1]
[实施例1-2]
在干燥氮气氛下,在具备回流装置和搅拌装置的5,000mL三口烧瓶中加入由下述式(18)表示的化合物1,237g、四甲基二硅氧烷443g、甲乙酮1,237g、甲磺酸18g,边搅拌边冷却到5℃。向其中滴入离子交换水48g,在将内部温度维持在0~10℃的状态下继续搅拌3小时。然后,加入水滑石(KYOWARD 500SH、协和化学工业(株)制造)88g,在将内部温度维持在0~10℃的状态下进行搅拌2小时,将溶剂、过剩的四甲基二硅氧烷减压馏除后,将水滑石过滤分离,得到了由下述式(19)表示的无色透明的液体1,256g。
[化36]
(式中,a2≥1、b2≥1、a2/b2=0.76,带有a2及b2的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
在干燥氮气氛下,对于化合物(19)363g,将烯丙氧基三甲基硅烷156g、甲苯436g、和氯铂酸/乙烯基硅氧烷络合物的甲苯溶液2.9g(以Pt单质计,含有7.3×10-5摩尔)混合,在80℃下搅拌2小时。通过1H-NMR测定及FT-IR测定确认了来自Si-H基的信号消失后,将溶剂和过剩的烯丙氧基三甲基硅烷减压馏除,进行了活性炭处理后,进行过滤,从而得到了由下述式(20)表示的淡黄色透明的液体410g。
[化37]
(式中,a2≥1、b2≥1、a2/b2=0.76,带有a2及b2的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
在干燥氮气氛下,对于化合物(20)230g,加入甲醇2,300g,在67℃下加热搅拌12小时,将副产的三甲基甲氧基硅烷常压馏除后,将过剩的甲醇和三甲基硅烷减压馏除,得到了由下述式(21)表示的淡黄色透明的液体180g。
[化38]
(式中,a2≥1、b2≥1、a2/b2=0.76,带有a2及b2的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
在干燥氮气氛下,对于化合物(21)133g,加入三乙胺34g、六氟间二甲苯663g,边搅拌边升温到60℃。边将内部温度维持在55~60℃,边向其中滴入将丙烯酰氯20g用甲苯40g稀释的混合物,继续搅拌30分钟。其次,在将内部温度维持在55~60℃的状态下滴入乙醇1.8g,继续搅拌1小时。将析出的盐过滤分离,在得到的滤液中加入水滑石(协和化学工业(株)制造、KYOWARD 500SH)7.4g和硅酸铝(协和化学工业(株)制造、KYOWARD 700)7.4g,搅拌2小时后,减压馏除,通过将水滑石和硅酸铝过滤分离,从而得到了淡黄色透明的液体102g。
通过1H-NMR测定确认了得到的生成物为由下述式(22)表示的含氟硅氧烷丙烯酸酯。将1H-NMR波谱的化学位移示于表2中。
[化39]
(式中,a2≥1、b2≥1、a2/b2=0.76,带有a2及b2的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
[表2]
[实施例1-3]
在干燥氮气氛下,对于上述化合物(19)121g,将烯丙二醇41g、甲苯121g和氯铂酸/乙烯基硅氧烷络合物的甲苯溶液0.85g(以Pt单质计,含有2.2×10-5摩尔)混合,在80℃下搅拌了2小时。通过1H-NMR测定及FT-IR测定确认了来自Si-H基的信号消失后,将溶剂和过剩的烯丙二醇减压馏除,进行了活性炭处理后,通过进行过滤,从而得到了由下述式(23)表示的淡黄色透明的液体122g。
[化40]
(式中,a2≥1、b2≥1、a2/b2=0.76,带有a2及b2的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
在干燥氮气氛下,对于化合物(23)141g,加入三乙胺27g、六氟间二甲苯707g,边搅拌边升温到60℃。边将内部温度维持在55~60℃,边向其中滴入将丙烯酰氯20g用甲苯40g稀释的混合物,继续搅拌30分钟。其次,在将内部温度维持在55~60℃的状态下滴入乙醇1.8g,继续搅拌1小时。将析出的盐过滤分离,在得到的滤液中加入水滑石(KYOWARD500SH、协和化学工业(株)制造)7.9g和硅酸铝(KYOWARD 700、协和化学工业(株)制造)7.9g,搅拌2小时后,减压馏除,通过将水滑石和硅酸铝过滤分离,从而得到了淡黄色透明的液体112g。
通过1H-NMR测定确认了得到的生成物为由下述式(24)表示的含氟硅氧烷丙烯酸酯。将1H-NMR波谱的化学位移示于表3中。
[化41]
(式中,a2≥1、b2≥1、a2/b2=0.76,带有a2及b2的括弧内的重复单元的排列是不定的,全氟聚醚链的数均分子量为1,500。)
[表3]
[比较例1-1]
由下述式(25)表示的含氟硅氧烷丙烯酸酯。
[化42]
(式中,a3≥1、b3≥1、a3/b3=0.76,带有a3和b3的括弧内的重复单元的排列不定,全氟聚醚链的数均分子量为2,000。)
对于实施例1-1~1-3、比较例1-1的含氟硅氧烷丙烯酸酯,采用下述方法进行了评价。将结果示于表4中。
[丙烯酰基当量]
基于采用1H-NMR波谱解析得到的结构,算出每1摩尔丙烯酰基的分子量。
[折射率]
在25℃下使用折射率计(装置名:RX-7000α、(株)アタゴ制造)测定。
[表4]
[实施例2-1~2-3、比较例2-1]
在甲基异丁基酮100质量份、4官能丙烯酸酯(A-TMMT、新中村化学工业(株)制造)100质量份、2-羟基-2-甲基-1-苯基丙酮(Omnirad 1173、IGM RESINS B.V.制造)2质量份中混合含氟硅氧烷丙烯酸酯(实施例1-1~1-3、比较例1-1)1质量份,分别制备了涂布组合物。
[比较例2-2]
除了不含含氟硅氧烷丙烯酸酯以外,与实施例2-1~2-3、比较例2-1同样地制备涂布组合物。
[组合物外观]
对于实施例2-1~2-3、比较例2-1、2-2的涂布组合物,通过目视评价了外观。将结果示于表5中。
[被膜外观]
将实施例2-1~2-3、比较例2-1、2-2的涂布组合物分别在聚碳酸酯板上旋涂,使用输送机型紫外线照射装置(EYEGRAPHICS(株)制造),在氮气氛中照射600mJ/cm 2的紫外线,形成固化膜,通过目视评价了外观。将结果示于表5中。
[水接触角、十六烷接触角]
对于上述被膜外观试验中作成的固化膜,使用接触角计(协和界面科学(株)制造)测定了水接触角、十六烷接触角。将结果示于表5。
[表5]
如表4中所示那样,实施例1-1~1-3的含氟硅氧烷丙烯酸酯与比较例1-1相比,虽然丙烯酰基当量(g/mol)小(每单位质量的丙烯酰基浓度大),但是具有更低的折射率。
另外,如表5中所示那样,可知本发明的含氟硅氧烷丙烯酸酯显示出与比较例1-1同等的外观、水接触角和十六烷接触角,具有溶解性及防污性。
如以上所述,本发明的含氟硅氧烷丙烯酸酯由于溶解性、低折射率、防污性优异,因此不仅可用作向玻璃、树脂、膜、纸、金属、陶器、木材等的涂布组合物、印刷物表面的保护膜用组合物、涂料添加剂,而且可用作用于低反射膜的添加剂。
Claims (9)
1.由下述式(1)表示的含氟硅氧烷丙烯酸酯:
X-Z-PFPE-Z-X (1)
式中,PFPE表示数均分子量500~30,000的2价的全氟聚醚链,X各自独立地为由下述式(2)表示的基团,
式(2)中,Y1各自独立地为由下述式表示的2价的有机基团,
*---CH2CH2CH2---
*---CH(CH3)CH2---
*---CH2CH2CH(CH3)CH2-----
*---CH2CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CH2CH2---
*---CH2CH2CH2-O-CH2CH2O-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2---
式中,虚线表示键合端,星号(*)表示与硅原子的键合部位,
R2各自独立地为氢原子、氟原子、甲基、或三氟甲基,G各自独立地为碳原子数1~12的烷基或由下述式(3)表示的基团,
式(3)中,R1为碳原子数1~12的1价烃基,Y1如上所述,虚线表示键合端,
Q为氢原子、或由下述式(4)表示的基团,
式(4)中,R3各自独立地为碳原子数1~12的1价烃基,虚线表示键合端,
e为0~2的整数,f为0~2的整数,g为1~3的整数,e+f+g为3,虚线表示键合端,
Z各自独立地为由下述式表示的2价的有机基团,
式中,虚线表示键合端,**标记表示与所述PFPE的键合部位。
2.根据权利要求1所述的含氟硅氧烷丙烯酸酯,其中,PFPE为由下述式表示的数均分子量1,000~5,000的全氟聚醚链,
---CF2(OCF2)a(OCF2CF2)bOCF2---(6)
式中,a为a≥1的数,b为b≥1的数,a/b为1/10~10/1的数,带有a及b的括弧内的重复单元的排列可为任意,虚线表示键合端。
3.根据权利要求1或2所述的含氟硅氧烷丙烯酸酯,Z为由下述式表示的2价的有机基团,
式中,虚线表示键合端,**标记表示与所述PFPE的键合部位。
4.根据权利要求1或2所述的含氟硅氧烷丙烯酸酯,其中,G为碳原子数1~6的烷基或由上述式(3)表示的基团,式(3)中的R1为甲基、乙基或正丙基,e为1或2。
5.根据权利要求4所述的含氟硅氧烷丙烯酸酯,其中,G为碳原子数1~3的烷基。
6.根据权利要求1或2所述的含氟硅氧烷丙烯酸酯,其中,e为0。
7.涂布组合物,其包含根据权利要求1~6中任一项所述的含氟硅氧烷丙烯酸酯。
8.根据权利要求7所述的涂布组合物,其还包含根据权利要求1~6中任一项所述的含氟硅氧烷丙烯酸酯以外的丙烯酸酯或氨基甲酸酯丙烯酸酯。
9.物品,其具有包括根据权利要求7或8所述的涂布组合物的固化物的被膜。
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