JP2011241190A - Fluorine-containing (meth)acrylic-modified organosilicon compound and curable composition containing the same - Google Patents
Fluorine-containing (meth)acrylic-modified organosilicon compound and curable composition containing the same Download PDFInfo
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- JP2011241190A JP2011241190A JP2010115979A JP2010115979A JP2011241190A JP 2011241190 A JP2011241190 A JP 2011241190A JP 2010115979 A JP2010115979 A JP 2010115979A JP 2010115979 A JP2010115979 A JP 2010115979A JP 2011241190 A JP2011241190 A JP 2011241190A
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- fluorine
- compound
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 61
- 239000011737 fluorine Substances 0.000 title claims abstract description 50
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 150000003961 organosilicon compounds Chemical class 0.000 title claims abstract description 38
- 238000007259 addition reaction Methods 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 17
- 125000004429 atom Chemical group 0.000 claims abstract description 10
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 128
- -1 siloxane structure Chemical group 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 125000001153 fluoro group Chemical group F* 0.000 claims description 11
- 239000010702 perfluoropolyether Substances 0.000 claims description 11
- 125000005647 linker group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 18
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 7
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000002904 solvent Substances 0.000 description 23
- 239000004593 Epoxy Substances 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 125000003700 epoxy group Chemical group 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical group 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 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 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-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
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 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 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000003808 silyl group Chemical class [H][Si]([H])([H])[*] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- 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 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- XLRHAAFCQUDHHF-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane;1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O.O=C=NCC(C)CC(C)(C)CCN=C=O XLRHAAFCQUDHHF-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 1
- COAUHYBSXMIJDK-UHFFFAOYSA-N 3,3-dichloro-1,1,1,2,2-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)C(Cl)Cl COAUHYBSXMIJDK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- NGZUCVGMNQGGNA-UHFFFAOYSA-N 7-[5-(2-acetamidoethyl)-2-hydroxyphenyl]-3,5,6,8-tetrahydroxy-9,10-dioxoanthracene-1,2-dicarboxylic acid 7-[5-(2-amino-2-carboxyethyl)-2-hydroxyphenyl]-3,5,6,8-tetrahydroxy-9,10-dioxoanthracene-1,2-dicarboxylic acid 3,5,6,8-tetrahydroxy-7-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-9,10-dioxoanthracene-1,2-dicarboxylic acid 3,6,8-trihydroxy-1-methyl-9,10-dioxoanthracene-2-carboxylic acid Chemical compound Cc1c(C(O)=O)c(O)cc2C(=O)c3cc(O)cc(O)c3C(=O)c12.OCCc1ccc(O)c(c1)-c1c(O)c(O)c2C(=O)c3cc(O)c(C(O)=O)c(C(O)=O)c3C(=O)c2c1O.CC(=O)NCCc1ccc(O)c(c1)-c1c(O)c(O)c2C(=O)c3cc(O)c(C(O)=O)c(C(O)=O)c3C(=O)c2c1O.NC(Cc1ccc(O)c(c1)-c1c(O)c(O)c2C(=O)c3cc(O)c(C(O)=O)c(C(O)=O)c3C(=O)c2c1O)C(O)=O NGZUCVGMNQGGNA-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- HZRPIZSSEMKEEW-UHFFFAOYSA-N C1CO1.O=C1NC(=O)NC(=O)N1 Chemical compound C1CO1.O=C1NC(=O)NC(=O)N1 HZRPIZSSEMKEEW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 150000004687 hexahydrates Chemical class 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
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- 239000002952 polymeric resin Substances 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
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- 239000002689 soil Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- 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
- 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
- C08F214/00—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 halogen
- C08F214/18—Monomers containing fluorine
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- 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
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- 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
- C09D183/16—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 in which all the silicon atoms are connected by linkages other than oxygen atoms
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Description
本発明は、光硬化可能なパーフルオロポリエーテル基を有する（メタ）アクリル変性有機ケイ素化合物に関し、更に詳述すると、含フッ素エポキシ変性有機ケイ素化合物と（メタ）アクリル基を有する不飽和モノカルボン酸との付加反応で得られる含フッ素（メタ）アクリル変性有機ケイ素化合物、これを含む硬化性組成物、及び紫外線又は電子線硬化型ハードコート組成物に関する。 The present invention relates to a (meth) acryl-modified organosilicon compound having a photocurable perfluoropolyether group, and more specifically, a fluorine-containing epoxy-modified organosilicon compound and an unsaturated monocarboxylic acid having a (meth) acryl group. The present invention relates to a fluorine-containing (meth) acryl-modified organosilicon compound obtained by an addition reaction with A, a curable composition containing the same, and an ultraviolet ray or electron beam curable hard coat composition.
従来、紫外線等の光照射により硬化可能なフッ素化合物としては、側鎖にパーフルオロアルキル基を有する重合性モノマー、例えば、アクリル酸含フッ素アルキルエステルやメタクリル酸含フッ素アルキルエステルを含む重合体が広く知られている。代表的なものとして、下記の構造のものが基材表面に撥水撥油性、防汚性、耐摩耗性、耐擦傷性等を付与する目的で多く用いられてきた。
ところが、近年、環境負荷の懸念から炭素数８以上の長鎖パーフルオロアルキル基を含有する化合物の利用を制限する動きが強まっている。しかしながら、炭素数８未満のパーフルオロアルキル基を含有するアクリル化合物は、炭素数８以上の長鎖パーフルオロアルキル基を持つものに比べ、その表面特性が顕著に悪いことが知られている（非特許文献１：高分子諭文集Ｖｏｌ．６４，Ｎｏ．４，ｐｐ．１８１−１９０）。 However, in recent years, there has been an increasing trend to limit the use of compounds containing a long-chain perfluoroalkyl group having 8 or more carbon atoms due to concerns about environmental burden. However, it is known that an acrylic compound containing a perfluoroalkyl group having less than 8 carbon atoms has significantly worse surface properties than those having a long-chain perfluoroalkyl group having 8 or more carbon atoms (non-non-volatile). Patent Document 1: Polymer Shukubun Vol.64, No. 4, pp.181-190).
一方、連続する炭素数が３以下のパーフルオロアルキル基とエーテル結合性酸素原子からなるパーフルオロポリエーテル類を導入した光硬化可能なフッ素化合物が知られている。例えば、ヘキサフルオロプロピレンオキシドオリゴマーから誘導される下記のアクリル化合物が提案されている（特許文献１：特開平５−１９４３２２号公報）。
また、フッ素含有ポリエーテルジオールと２−イソシアネートエチルメタクリレートとの反応物からなるウレタンアクリレートが提案されている（特許文献２：特開平１１−３４９６５１号公報）。しかし、フッ素含有化合物の撥水撥油特性から、光重合開始剤、非フッ素化アクリレート、及び非フッ素化有機溶剤との相溶性が低く、配合可能な成分及び用途が限定的であった。 Further, a urethane acrylate comprising a reaction product of a fluorine-containing polyether diol and 2-isocyanate ethyl methacrylate has been proposed (Patent Document 2: Japanese Patent Application Laid-Open No. 11-349651). However, the water- and oil-repellent properties of fluorine-containing compounds have low compatibility with photopolymerization initiators, non-fluorinated acrylates, and non-fluorinated organic solvents, and the components and applications that can be blended are limited.
本発明は、上記事情に鑑みなされたものであり、フッ素化合物の優れた特性を有すると共に、非フッ素系有機化合物との相溶性、硬化性に優れた含フッ素（メタ）アクリル変性有機ケイ素化合物、これを含む硬化性組成物、及び紫外線又は電子線硬化型ハードコート組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, and has a fluorine-containing (meth) acryl-modified organosilicon compound having excellent characteristics of a fluorine compound, compatibility with a non-fluorine organic compound, and excellent curability, It aims at providing the curable composition containing this, and an ultraviolet-ray or an electron beam hardening type hard-coat composition.
本発明者らは、上記目的を達成するため鋭意検討した結果、含フッ素化合物の末端に、多官能Ｓｉ−Ｈ化合物（例えば、多官能（即ち、３個以上）のＳｉＨ基を含有する、シロキサン、シルアルキレン、シルアリーレン又はこれらの２種以上の組み合せからなる有機ケイ素化合物）を導入し、ここに末端不飽和結合とエポキシ基を有する炭化水素化合物を付加させて得られる化合物（Ａ）に対して、更に導入されたエポキシ基にアクリル酸等の（メタ）アクリル基を有する不飽和カルボン酸（Ｂ）を反応させることで、撥水、撥油、防汚性に優れる含フッ素基のセグメントを、非フッ素化有機化合物との溶解性に優れる水酸基やエポキシ基を含むスペーサー構造を介することでアクリル基と同一分子中で結合させることができ、上記目的に一致する化合物が合成可能なことを見出し、本発明をなすに至った。 As a result of diligent studies to achieve the above object, the present inventors have found that a siloxane containing a polyfunctional Si—H compound (for example, a polyfunctional (ie, 3 or more) SiH group) at the terminal of the fluorine-containing compound. , Silalkylene, silarylene, or a combination of two or more thereof, and a hydrocarbon compound having a terminal unsaturated bond and an epoxy group is added to the compound (A). Further, by reacting the introduced epoxy group with an unsaturated carboxylic acid (B) having a (meth) acrylic group such as acrylic acid, a segment of a fluorine-containing group having excellent water repellency, oil repellency and antifouling properties can be obtained. It can be bonded in the same molecule as the acrylic group through a spacer structure containing a hydroxyl group or an epoxy group that is excellent in solubility with a non-fluorinated organic compound. Compounds that are found to be capable of combining, the present invention has been accomplished.
従って、本発明は、下記含フッ素（メタ）アクリル変性有機ケイ素化合物、これを含む硬化性組成物、及び紫外線又は電子線硬化型ハードコート組成物を提供する。
請求項１：
（Ａ）下記一般式（１）
で表される含フッ素エポキシ変性有機ケイ素化合物に、（Ｂ）（メタ）アクリル基を有する不飽和モノカルボン酸を付加反応させることにより得られた含フッ素（メタ）アクリル変性有機ケイ素化合物。
請求項２：
一般式（１）において、Ｒｆが、下記式
−ＣiＦ2iＯ−
（ｉは、単位毎に独立に、１〜６の整数である。）
で表される繰り返し単位を１〜５００個含むことを特徴とする請求項１記載の化合物。
請求項３：
一般式（１）において、Ｑ1が、下記式（２）
で示される基と結合する。また、２種類の繰り返し単位の並びはランダムである。Ｒｆは式（１）で定義した通りである。）
で表される請求項１又は２記載の化合物。
請求項４：
一般式（１）において、Ｒｆが、下記一般式（３）
−［Ｑ3−Ｒｆ’−Ｑ3−Ｔ］v−Ｑf−Ｒｆ’−Ｑ3− （３）
（但し、Ｒｆ’は二価の分子量３００〜３０，０００のパーフルオロポリエーテル基であり、途中分岐を含んでいても良い。Ｑ3は二価の有機基であり、酸素原子、窒素原子、フッ素原子又はケイ素原子を含んでいてもよく、また、環状構造又は不飽和結合を有する基であってもよい。ＱfはＱ3又はフッ素原子である。Ｔは、下記式（４）
で表される連結基であり、ｖは０〜５の整数であり、なおかつＱfがフッ素原子のときｖ＝０である。）
で表される請求項１〜３のいずれか１項記載の化合物。
請求項５：
請求項１〜４のいずれか１項に記載の含フッ素（メタ）アクリル変性有機ケイ素化合物を含有することを特徴とする硬化性組成物。
請求項６：
請求項１〜４のいずれか１項に記載の含フッ素（メタ）アクリル変性有機ケイ素化合物を含有することを特徴とする紫外線又は電子線硬化型ハードコート組成物。
Accordingly, the present invention provides the following fluorine-containing (meth) acryl-modified organosilicon compound, a curable composition containing the same, and an ultraviolet ray or electron beam curable hard coat composition.
Claim 1:
(A) The following general formula (1)
(B) A fluorine-containing (meth) acryl-modified organosilicon compound obtained by subjecting an unsaturated monocarboxylic acid having a (meth) acryl group to an addition reaction to a fluorine-containing epoxy-modified organosilicon compound represented by the formula:
Claim 2:
In the general formula (1), Rf represents the following formula -C i F 2i O-
(I is an integer of 1 to 6 independently for each unit.)
The compound according to claim 1, comprising 1 to 500 repeating units represented by the formula:
Claim 3:
In the general formula (1), Q 1 represents the following formula (2)
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. Rf is as defined in Formula (1). )
The compound of Claim 1 or 2 represented by these.
Claim 4:
In general formula (1), Rf is the following general formula (3)
− [Q 3 −Rf′−Q 3 −T] v −Q f −Rf′−Q 3 − (3)
(However, Rf ′ is a divalent perfluoropolyether group having a molecular weight of 300 to 30,000, and may contain a branch in the middle. Q 3 is a divalent organic group, and includes an oxygen atom, a nitrogen atom, It may contain a fluorine atom or a silicon atom, and may be a group having a cyclic structure or an unsaturated bond, Q f is Q 3 or a fluorine atom, T is the following formula (4)
Wherein v is an integer of 0 to 5 and v = 0 when Q f is a fluorine atom. )
The compound of any one of Claims 1-3 represented by these.
Claim 5:
A curable composition comprising the fluorine-containing (meth) acryl-modified organosilicon compound according to any one of claims 1 to 4.
Claim 6:
An ultraviolet or electron beam curable hard coat composition comprising the fluorine-containing (meth) acryl-modified organosilicon compound according to any one of claims 1 to 4.
本発明の含フッ素（メタ）アクリル変性有機ケイ素化合物は、非フッ素化有機化合物との相溶性に優れるだけでなく、光で硬化して撥水撥油性の硬化物を形成することができ、ハードコート用の防汚添加剤として有用である。 The fluorine-containing (meth) acryl-modified organosilicon compound of the present invention not only has excellent compatibility with non-fluorinated organic compounds, but also can be cured by light to form a water- and oil-repellent cured product. Useful as an antifouling additive for coatings.
以下、本発明を詳細に説明する。
本発明に係る含フッ素（メタ）アクリル変性有機ケイ素化合物は、（Ａ）下記一般式（１）
で表される含フッ素エポキシ変性有機ケイ素化合物に、（Ｂ）（メタ）アクリル基を有する不飽和モノカルボン酸を付加反応させることにより得られる含フッ素（メタ）アクリル変性有機ケイ素化合物である。
Hereinafter, the present invention will be described in detail.
The fluorine-containing (meth) acryl-modified organosilicon compound according to the present invention comprises (A) the following general formula (1)
(B) A fluorine-containing (meth) acryl-modified organosilicon compound obtained by subjecting an unsaturated monocarboxylic acid having a (meth) acryl group to an addition reaction to the fluorine-containing epoxy-modified organosilicon compound represented by formula (1).
ここで、Ｑ1は少なくとも（ａ＋ｂ）個のＳｉ原子を有する（ａ＋ｂ）価のシロキサン構造、非置換又はハロゲン置換のシルアルキレン構造、シルアリーレン構造又はこれらの２種以上の組み合せからなる連結基であり、環状構造をなしていてもよく、具体的には以下の構造が示される。但し、下記式中、ａ、ｂは前述の定義通りであり、好ましくはａ、ｂ共に１〜４の整数であり、かつａ＋ｂは３〜５の整数である。ｐは０以上の任意の正の整数であり、ａ個及びｂ個の各ユニットの並びはランダムであり、ａ個及びｂ個の各ユニットの破線で示される結合手は、Ｒｆ又は下記式
で示されるいずれか一方の基と結合する。
Here, Q 1 is a linking group composed of an (a + b) -valent siloxane structure having at least (a + b) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof. Yes, it may have a ring structure, and specifically, the following structure is shown. However, in the following formula, a and b are as defined above, preferably both a and b are integers of 1 to 4, and a + b is an integer of 3 to 5. p is an arbitrary positive integer of 0 or more, the arrangement of each of the a and b units is random, and the bond shown by the broken line of each of the a and b units is Rf or the following formula
It couple | bonds with either group shown by.
ここで、Ｑ5は（ａ＋ｂ）価の連結基であり、例えば以下のものが例示される。
Here, Q 5 is an (a + b) -valent linking group, and examples thereof include the following.
Ｑ2は炭素数１〜２０、好ましくは２〜１５の二価の炭化水素基であり、環状構造をなしていてもよく、途中エーテル結合（−Ｏ−）又はエステル結合（−ＣＯＯ−）を含んでいてもよい。具体的には、下記構造のものが挙げられる。
−ＣＨ2ＣＨ2−
−ＣＨ2ＣＨ（ＣＨ3）−
−ＣＨ2ＣＨ2ＣＨ2ＣＨ2−
−ＣＨ2ＣＨ2（ＣＨ2）6−
−ＣＨ2ＣＨ2ＣＨ2ＯＣＨ2−
−ＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＨ（ＣＨ3）−
Q 2 is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and may have a cyclic structure, and an ether bond (—O—) or ester bond (—COO—) is formed on the way. May be included. Specifically, the following structures are exemplified.
—CH 2 CH 2 —
-CH 2 CH (CH 3) -
—CH 2 CH 2 CH 2 CH 2 —
—CH 2 CH 2 (CH 2 ) 6 —
-CH 2 CH 2 CH 2 OCH 2 -
-CH 2 CH 2 CH 2 OCH 2 CH (CH 3) -
Ｒ1〜Ｒ3はそれぞれ独立に水素原子又は炭素数１〜１０、好ましくは１〜８の一価炭化水素基であり、これらの基の水素原子の一部又は全部がフッ素原子等のハロゲン原子で置換されていても良く、Ｒ1とＲ2が結合してこれらが結合する炭素原子と共に、シクロヘキシル環等の炭素数３〜８の一つの環をなしていても良い。Ｒ1〜Ｒ3の具体例としては、水素原子、メチル基、エチル基、プロピル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基等が挙げられる。このようなＲ1〜Ｒ3とＱ2の組み合わせからなる一般式（１）中の下記式
が挙げられる。また、上記式の代わりに、下記式
で示される基を用いることもでき、具体例としては、
Is mentioned. Also, instead of the above formula, the following formula
It is also possible to use a group represented by
Ｒｆはフルオロアルキル構造又はフルオロポリエーテル構造を含む一価又は二価の基であり、Ｒｆとしての分子量は１００〜４０，０００、好ましくは５００〜２０，０００で、なおかつ下記式
−ＣiＦ2iＯ−
（ｉは、単位毎に独立に、１〜６の整数である。）
で表される繰り返し単位を１〜５００個、好ましくは２〜４００個、更に好ましくは４〜２００個含むものが好適である。なお、本発明において、分子量は、1Ｈ−ＮＭＲ及び19Ｆ−ＮＭＲに基づく末端構造と主鎖構造との比率から算出される数平均分子量である。
Rf is a monovalent or divalent group containing a fluoroalkyl structure or a fluoropolyether structure, the molecular weight as Rf is 100 to 40,000, preferably 500 to 20,000, and the following formula —C i F 2i O-
(I is an integer of 1 to 6 independently for each unit.)
Those containing 1 to 500, preferably 2 to 400, more preferably 4 to 200 repeating units represented by formula (1) are suitable. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio between the terminal structure and the main chain structure based on 1 H-NMR and 19 F-NMR.
Ｒｆとして特に好ましい構造を下記一般式（３）で表すことができる。
−［Ｑ3−Ｒｆ’−Ｑ3−Ｔ］v−Ｑf−Ｒｆ’−Ｑ3− （３）
Ｒｆ’は二価の分子量３００〜３０，０００、特に５００〜２０，０００のパーフルオロポリエーテル基であり、途中分岐を含んでいても良く、特に下記式（５）〜（７）で表される二価のパーフルオロポリエーテル基が好ましい。
− [Q 3 −Rf′−Q 3 −T] v −Q f −Rf′−Q 3 − (3)
Rf ′ is a perfluoropolyether group having a divalent molecular weight of 300 to 30,000, particularly 500 to 20,000, and may contain a middle branch, particularly represented by the following formulas (5) to (7). Divalent perfluoropolyether groups are preferred.
Ｑ3は二価の有機基であり、酸素原子、窒素原子、フッ素原子又はケイ素原子を含んでいてもよく、また、環状構造あるいは不飽和結合を有する基であってもよい。ＱfはＱ3又はフッ素原子である。このようなＱ3としては下記のものが例示される。なお、式中、Ｐｈはフェニル基を示す。 Q 3 is a divalent organic group, may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom, and may be a group having a cyclic structure or an unsaturated bond. Q f is Q 3 or a fluorine atom. Examples of such Q 3 include the following. In the formula, Ph represents a phenyl group.
これらのなかでも特に
また、Ｔは、下記式（４）
で表される二価の連結基である。また、ｖは０〜５の整数であり、なおかつＱfがフッ素原子のときｖ＝０である。
T is the following formula (4)
It is a bivalent coupling group represented by these. Also, v is an integer from 0 to 5, and yet Q f is v = 0 when the fluorine atoms.
ａ及びａ’は、Ｒｆが一価のときにはａ’は１であり、かつａは１〜６、特に１〜３の整数であり、Ｒｆが二価のときにはａは１であり、かつａ’は２である。ｂは１〜２０、特に１〜６の整数である。ａ＋ｂは３〜６の整数が好ましい。 a and a ′ are a ′ of 1 when Rf is monovalent, and a is an integer of 1 to 6, particularly 1 to 3, a is 1 when Rf is divalent, and a ′ Is 2. b is an integer of 1 to 20, particularly 1 to 6. a + b is preferably an integer of 3 to 6.
Ｒｆの具体例としては、下記のものが挙げられる。
以上のような一般式（１）で表される含フッ素エポキシ変性有機ケイ素化合物（Ａ）は、例えば次のような方法で合成することが可能である。
まず初めに、末端にオレフィン基を有する含フッ素化合物（ａ）に対して、多官能Ｓｉ−Ｈ化合物（例えば、分子中に２個以上、好ましくは３個以上のＳｉ−Ｈ基を有するシロキサン、シルアルキレン、シルアリーレン又はこれらの２種以上の組み合せからなる有機ケイ素化合物）（ｂ）をＳｉ−Ｈ基が過剰の条件下でヒドロシリル化付加反応させ、含フッ素多官能Ｓｉ−Ｈ化合物（ｃ）を合成する。
The fluorine-containing epoxy-modified organosilicon compound (A) represented by the general formula (1) as described above can be synthesized, for example, by the following method.
First, with respect to the fluorine-containing compound (a) having an olefin group at the terminal, a polyfunctional Si—H compound (for example, a siloxane having 2 or more, preferably 3 or more Si—H groups in the molecule, (Silalkylene, silarylene, or an organosilicon compound composed of a combination of two or more thereof) (b) is subjected to a hydrosilylation addition reaction under an excessive Si-H group condition to produce a fluorine-containing polyfunctional Si-H compound (c) Is synthesized.
このような化合物（ａ）のうち、特に望ましい構造を一般化した例として下記式（８）を示すことができる。
Ｒｆ0−（ＣＨ＝ＣＨ2）x （８）
ここで、Ｒｆ0は下記式
−［Ｑ6−Ｒｆ’−Ｑ3−Ｔ］v−Ｑf−Ｒｆ’−Ｑ6−
で表される。上記式中、Ｒｆ’、Ｔ、Ｑf、Ｑ3、ｖは上述した通りであり、Ｑ6は二価の有機基であり、酸素原子、窒素原子、フッ素原子又はケイ素原子を含んでいてもよく、また、環状構造又は不飽和結合を有する基であってもよい。ｘはＲｆ0が一価のとき１、二価のとき２である。
Among such compounds (a), the following formula (8) can be shown as an example of generalizing a particularly desirable structure.
Rf 0 − (CH═CH 2 ) x (8)
Here, Rf 0 is represented by the following formula-[Q 6 -Rf′-Q 3 -T] v -Q f -Rf′-Q 6-
It is represented by In the above formula, Rf ′, T, Q f , Q 3 and v are as described above, Q 6 is a divalent organic group, and may contain an oxygen atom, a nitrogen atom, a fluorine atom or a silicon atom. It may also be a group having a cyclic structure or an unsaturated bond. x is 1 when Rf 0 is monovalent and 2 when Rf 0 is divalent.
Ｑ6としては、下記例が挙げられる。なお、下記例中、Ｐｈはフェニル基を示す。
化合物（ａ）の特に好ましいものとして、以下のものが例示できる。
また、化合物（ｂ）は下記式（９）のような形で一般式として表現できる。
Ｑ1−（Ｈ）a+b （９）
（但し、Ｑ1、ａ、ｂは前述の通りであり、かっこ内に示されたＨはＱ1構造中のＳｉ原子に直接結合した水素原子である。）
The compound (b) can be expressed as a general formula in the form of the following formula (9).
Q 1 − (H) a + b (9)
(However, Q 1 , a, and b are as described above, and H shown in parentheses is a hydrogen atom directly bonded to an Si atom in the Q 1 structure.)
このようなもののうち好ましい化合物（ｂ）としては、以下のものが例示できる。
以上のような化合物（ａ）及び（ｂ）を任意の組み合わせで、白金族金属系の付加反応触媒存在下、反応温度６０〜１５０℃、好ましくは７０〜１２０℃で付加反応を行うことで含フッ素多官能Ｓｉ−Ｈ化合物（ｃ）を得ることができる。
例えば、化合物（ａ）が１官能性の場合（式（８）においてｘ＝１）、化合物（ｂ）１分子に対して付加させる化合物（ａ）の数は（ａ＋ｂ）個未満であれば１個でも、複数個でも問題なく、例えばａ個付加させた場合に得られる化合物（ｃ）は次のような一般式（１０）で表すことができる。
（Ｒｆ0−Ｃ2Ｈ4）a−Ｑ1−（Ｈ）b （１０）
（Ｒｆ0、Ｑ1、ａ、ｂは上述した通りである。）
The compounds (a) and (b) as described above are contained in any combination in the presence of a platinum group metal addition reaction catalyst at a reaction temperature of 60 to 150 ° C., preferably 70 to 120 ° C. A fluorine polyfunctional Si—H compound (c) can be obtained.
For example, when the compound (a) is monofunctional (x = 1 in the formula (8)), 1 is added if the number of compounds (a) to be added to one molecule of the compound (b) is less than (a + b). For example, the compound (c) obtained when a number is added can be represented by the following general formula (10).
(Rf 0 -C 2 H 4 ) a -Q 1- (H) b (10)
(Rf 0 , Q 1 , a, and b are as described above.)
一方、化合物（ａ）が２官能性の場合には（式（８）においてｘ＝２）、（ａ）：（ｂ）＝ｖ＋１：ｖ＋２の比率（モル比）で付加させることが望ましく（ｖは前述の通りである。）、化合物（ｃ）は例えば式（１１）のように表現でき、ｖ＝０のときは化合物（ａ）の両末端に１分子ずつの化合物（ｂ）が導入された構造となる。
（Ｈ）b−Ｑ1−［Ｃ2Ｈ4−Ｒｆ0−Ｃ2Ｈ4−Ｔ2］v−
−Ｃ2Ｈ4−Ｒｆ0−Ｃ2Ｈ4−Ｑ1−（Ｈ）b
（１１）
（但し、Ｔ2は
である。
On the other hand, when the compound (a) is bifunctional (x = 2 in the formula (8)), it is desirable to add at a ratio (molar ratio) of (a) :( b) = v + 1: v + 2 (v The compound (c) can be expressed as, for example, the formula (11), and when v = 0, one molecule of the compound (b) is introduced at both ends of the compound (a). Structure.
(H) b -Q 1- [C 2 H 4 -Rf 0 -C 2 H 4 -T 2 ] v-
-C 2 H 4 -Rf 0 -C 2 H 4 -Q 1 - (H) b
(11)
(However, T 2 is
It is.
上記の付加反応は溶剤が存在しなくても実施可能であるが、必要に応じて溶剤で希釈しても良い。このとき希釈溶剤はトルエン、キシレン、イソオクタンなど広く一般に用いられている有機溶剤を利用することができるが、沸点が目的とする反応温度以上でかつ反応を阻害せず、反応後に生成する化合物（ｃ）が反応温度において可溶であることが好ましい。例えば、ｍ−キシレンヘキサフロライド、ベンゾトリフロライド等のフッ素変性芳香族炭化水素系溶剤、メチルパーフルオロブチルエーテル等のフッ素変性エーテル系溶剤等の部分フッ素変性された溶剤が望ましく、特にｍ−キシレンヘキサフロライドが好ましい。 The above addition reaction can be carried out in the absence of a solvent, but may be diluted with a solvent as necessary. At this time, a widely used organic solvent such as toluene, xylene, and isooctane can be used as the diluting solvent. However, the boiling point is not lower than the target reaction temperature and does not inhibit the reaction. ) Is preferably soluble at the reaction temperature. For example, a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluoride or benzotrifluoride or a fluorine-modified ether solvent such as methyl perfluorobutyl ether is desirable. Hexafluoride is preferred.
付加反応触媒は、例えば白金、ロジウム又はパラジウムを含む化合物を使用することができる。中でも白金を含む化合物が好ましく、ヘキサクロロ白金（ＩＶ）酸六水和物、白金カルボニルビニルメチル錯体、白金−ジビニルテトラメチルジシロキサン錯体、白金−シクロビニルメチルシロキサン錯体、白金−オクチルアルデヒド／オクタノール錯体、あるいは活性炭に担持された白金を用いることができる。触媒の配合量は、化合物（ａ）に対し、含まれる金属量が０．１〜５，０００質量ｐｐｍとなることが好ましく、より好ましくは１〜１，０００質量ｐｐｍである。 As the addition reaction catalyst, for example, a compound containing platinum, rhodium or palladium can be used. Among them, a compound containing platinum is preferable, hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Alternatively, platinum supported on activated carbon can be used. The compounding amount of the catalyst is preferably such that the amount of metal contained is 0.1 to 5,000 mass ppm, more preferably 1 to 1,000 mass ppm with respect to the compound (a).
付加反応において、各成分の仕込み順序は特に制限されないが、例えば化合物（ａ）、化合物（ｂ）及び触媒の混合物を室温から徐々に付加反応温度まで加熱する方法、化合物（ａ）、化合物（ｂ）及び希釈溶媒の混合物を目的とする反応温度にまで加熱した後に触媒を添加する方法、目的とする反応温度まで加熱した化合物（ｂ）と触媒の混合物に化合物（ａ）を滴下する方法、目的とする反応温度まで加熱した化合物（ｂ）に化合物（ａ）と触媒の混合物を滴下する方法等をとることができる。この中でも、化合物（ａ）、化合物（ｂ）及び希釈溶媒の混合物を目的とする反応温度にまで加熱した後に触媒を添加する方法、あるいは、目的とする反応温度まで加熱した化合物（ｂ）に化合物（ａ）と触媒の混合物を滴下する方法が特に好ましい。これらの方法は、各成分あるいは混合物を必要に応じて溶剤で希釈して用いることができる。上記反応は、乾燥雰囲気下で、空気あるいは不活性ガス（Ｎ2、Ａｒ等）中、反応温度６０〜１５０℃、好ましくは７０〜１２０℃で、０．５〜９６時間、好ましくは１〜４８時間行うことが望ましい。 In the addition reaction, the order in which the components are charged is not particularly limited. For example, the method of gradually heating the mixture of the compound (a), the compound (b) and the catalyst from room temperature to the addition reaction temperature, the compound (a), the compound (b ) And a dilute solvent mixture after heating to the target reaction temperature, adding the catalyst, dropping the compound (a) to the mixture of the compound (b) and catalyst heated to the target reaction temperature, The method of dripping the mixture of a compound (a) and a catalyst etc. to the compound (b) heated to reaction temperature to make can be taken. Among them, a method of adding a catalyst after heating a mixture of the compound (a), the compound (b) and the diluting solvent to a target reaction temperature or a compound (b) heated to a target reaction temperature. A method of dropping the mixture of (a) and the catalyst is particularly preferable. These methods can be used by diluting each component or mixture with a solvent as necessary. The above reaction is carried out in a dry atmosphere in air or an inert gas (N 2 , Ar, etc.) at a reaction temperature of 60 to 150 ° C., preferably 70 to 120 ° C., for 0.5 to 96 hours, preferably 1 to 48. It is desirable to do time.
化合物（ａ）に対する、化合物（ｂ）の配合量は、化合物（ｂ）１分子に対して、付加させる化合物（ａ）の数は（ａ＋ｂ）個未満で、かつ化合物（ｃ）におけるｖが０〜５の整数となる条件であればどのような配合量であってもよいが、三次元架橋を防ぐため、化合物（ａ）のアリル基等の末端オレフィン基に対し、化合物（ｂ）を過剰量用いて付加反応を行った後に、未反応の化合物（ｂ）を減圧留去等により除去することが望ましく、化合物（ａ）のアリル基等の末端オレフィン基１当量に対し、化合物（ｂ）を１〜１０当量、特に２〜６当量の存在下で反応させるのが好ましい。また必要に応じて、ｖが小さい中間体を合成してから、段階的に付加反応を行っても良い。例えばｖ＝０の化合物（１１）を合成した後に、２モルの化合物（１１）に対して、１モルの化合物（ａ）を再度反応させることでｖ＝３の化合物（ｃ）を得ることができる。あるいは、ｖの異なる混合物中から任意の分離手段により目的とするｖの値を持つ成分を分離することもできる。例えば、ｖ＝０〜３の混合物から、分取クロマトグラフ等の手段によりｖ＝１の成分のみを取り出しても良い。 The compounding amount of the compound (b) with respect to the compound (a) is such that the number of compounds (a) to be added is less than (a + b) per molecule of the compound (b), and v in the compound (c) is 0. Any amount may be used as long as it is an integer of ˜5, but in order to prevent three-dimensional crosslinking, compound (b) is excessive with respect to the terminal olefin group such as an allyl group of compound (a). It is desirable to remove the unreacted compound (b) by distillation under reduced pressure or the like after the addition reaction using an amount, and the compound (b) with respect to 1 equivalent of a terminal olefin group such as an allyl group of the compound (a). Is preferably reacted in the presence of 1 to 10 equivalents, particularly 2 to 6 equivalents. Further, if necessary, an addition reaction may be performed stepwise after synthesizing an intermediate having a small v. For example, after synthesizing compound (11) with v = 0, 1 mol of compound (a) is reacted again with 2 mol of compound (11) to obtain compound (c) with v = 3. it can. Alternatively, a component having a target value of v can be separated from a mixture having different v values by any separation means. For example, you may take out only the component of v = 1 from a mixture of v = 0-3 by means, such as a preparative chromatograph.
本発明で用いられる含フッ素エポキシ変性有機ケイ素化合物（Ａ）は、以上のようにして得られる化合物（ｃ）のＳｉ−Ｈ基と、一分子中に末端オレフィン基とエポキシ基を有する化合物（ｄ）との付加反応を行うことで、得ることができる。このような化合物（ｄ）としては、特に以下のものが好ましい。これらの化合物（ｄ）は１種単独で又は任意の２種以上を組み合わせても用いることができる。
化合物（ｃ）と化合物（ｄ）の付加反応は、前述した化合物（ａ）と化合物（ｂ）の付加反応と同様の手法で行うことができる。即ち、上述した付加反応触媒存在下、乾燥雰囲気下で、空気あるいは不活性ガス（Ｎ2、Ａｒ等）中、反応温度６０〜１５０℃、好ましくは７０〜１２０℃で０．５〜９６時間、好ましくは１〜４８時間、必要に応じて希釈を行い任意の添加順序での反応を実施することができるが、エポキシ基の熱による開環反応を防ぐため１００℃以下で行うことが望ましい。 The addition reaction of the compound (c) and the compound (d) can be performed by the same method as the addition reaction of the compound (a) and the compound (b) described above. That is, in the presence of the above-mentioned addition reaction catalyst, in a dry atmosphere, in air or an inert gas (N 2 , Ar, etc.), a reaction temperature of 60 to 150 ° C., preferably 70 to 120 ° C., for 0.5 to 96 hours, Preferably, the reaction can be carried out in any order of addition by dilution as necessary for 1 to 48 hours, but it is desirable to carry out the reaction at 100 ° C. or lower in order to prevent the ring-opening reaction due to heat of the epoxy group.
化合物（ｃ）に対する、化合物（ｄ）の配合量は任意の値を用いることができるが、化合物（ｃ）のＳｉ−Ｈ基に対して、化合物（ｄ）を等モルもしくは過剰量用いて付加反応を行った後に、未反応の化合物（ｄ）を減圧留去等により除去することが望ましく、化合物（ｃ）のＳｉ−Ｈ基１当量に対し、化合物（ｄ）を１．０〜２．０好ましくは１．０〜１．２当量存在下で反応を行うことが望ましい。 The compounding amount of the compound (d) with respect to the compound (c) can be any value, but the compound (d) is added in an equimolar amount or an excess amount with respect to the Si—H group of the compound (c). After the reaction, it is desirable to remove the unreacted compound (d) by distillation under reduced pressure or the like, and the compound (d) is added to 1.0 to 2. with respect to 1 equivalent of the Si—H group of the compound (c). It is desirable to carry out the reaction in the presence of 0, preferably 1.0 to 1.2 equivalents.
本発明においては、含フッ素エポキシ変性有機ケイ素化合物（Ａ）は、上記手法以外に、下記式
（Ｈ）b−Ｑ1−Ｒｆ
（Ｑ1、ｂ及びＲｆは上述した通りである。）
で示される含フッ素有機ケイ素化合物（ｅ）と、一分子中に末端オレフィン基とエポキシ基を有する化合物（ｄ）との付加反応を行うことで得ることもできる。この場合、反応条件等は上述した化合物（ｃ）と化合物（ｄ）との反応条件と同様とすることができる。
In the present invention, the fluorine-containing epoxy-modified organosilicon compound (A) is represented by the following formula (H) b -Q 1 -Rf in addition to the above method.
(Q 1 , b and Rf are as described above.)
It can also be obtained by carrying out an addition reaction between the fluorine-containing organosilicon compound (e) represented by the formula (d) and the compound (d) having a terminal olefin group and an epoxy group in one molecule. In this case, the reaction conditions and the like can be the same as the reaction conditions for the compound (c) and the compound (d) described above.
このようにして得られる含フッ素エポキシ変性有機ケイ素化合物（Ａ）として特に好ましい構造として、例えば以下のものを例示できる。 As a particularly preferable structure as the fluorine-containing epoxy-modified organosilicon compound (A) thus obtained, for example, the following can be exemplified.
本発明の含フッ素（メタ）アクリル変性有機ケイ素化合物は、このように表される含フッ素エポキシ変性有機ケイ素化合物（Ａ）に、（メタ）アクリル基を有する不飽和モノカルボン酸（Ｂ）を付加反応させた構造を有する。ここで、（メタ）アクリル基を有する不飽和モノカルボン酸（Ｂ）としては、アクリル酸、メタクリル酸が好適であるが、２−クロロアクリル酸、２−（トリフルオロメチル）アクリル酸、２，３，３−トリフルオロアクリル酸等のように一部の水素原子が塩素、フッ素等のハロゲン原子でハロゲン化されているものを用いることもできる。また、必要に応じてこれらのカルボン酸がアリル基、シリル基等で保護されたものを用いることもできる。これら不飽和モノカルボン酸は、１種単独で又は２種以上を組み合わせて用いることができる。 The fluorine-containing (meth) acryl-modified organosilicon compound of the present invention is obtained by adding an unsaturated monocarboxylic acid (B) having a (meth) acryl group to the fluorine-containing epoxy-modified organosilicon compound (A) represented as described above. It has a reacted structure. Here, as the unsaturated monocarboxylic acid (B) having a (meth) acrylic group, acrylic acid and methacrylic acid are preferable, but 2-chloroacrylic acid, 2- (trifluoromethyl) acrylic acid, 2, It is also possible to use those in which some hydrogen atoms are halogenated with halogen atoms such as chlorine and fluorine, such as 3,3-trifluoroacrylic acid. Moreover, what protected these carboxylic acids by the allyl group, the silyl group, etc. can also be used as needed. These unsaturated monocarboxylic acids can be used singly or in combination of two or more.
本発明における含フッ素（メタ）アクリル変性有機ケイ素化合物は、含フッ素エポキシ変性有機ケイ素化合物（Ａ）のエポキシ基と（メタ）アクリル基を有する不飽和モノカルボン酸（Ｂ）のカルボキシル基とを反応させて得られる。ここで、含フッ素エポキシ変性有機ケイ素化合物（Ａ）と（メタ）アクリル基を有する不飽和モノカルボン酸（Ｂ）の反応比率は、化合物（Ａ）１分子に対して化合物（Ｂ）を１分子以上の比率であれば特に制限されるものではなく、化合物（Ａ）に含まれる全エポキシ基に対して化合物（Ｂ）を全て反応させてもよく、逆にその一部のみ反応させて、含フッ素（メタ）アクリル変性有機ケイ素化合物の構造中のエポキシ基を残存させても良い。また、反応の際には、化合物（Ａ）に含まれる全エポキシ基に対して化合物（Ｂ）を等量もしくは過剰に仕込んで反応を行い、反応が目的の反応率に達した時点で停止させる手法も用いることができる。とりわけ、化合物（Ａ）のエポキシ基１当量に対して、化合物（Ｂ）を０．５〜２．０当量、特に０．８〜１．１当量用いることが好ましい。 The fluorine-containing (meth) acryl-modified organosilicon compound in the present invention reacts the epoxy group of the fluorine-containing epoxy-modified organosilicon compound (A) with the carboxyl group of the unsaturated monocarboxylic acid (B) having a (meth) acryl group. Can be obtained. Here, the reaction ratio of the fluorine-containing epoxy-modified organosilicon compound (A) and the unsaturated monocarboxylic acid (B) having a (meth) acryl group is one molecule of the compound (B) with respect to one molecule of the compound (A). If it is the above ratio, it will not restrict | limit in particular, All compounds (B) may be made to react with respect to all the epoxy groups contained in a compound (A), conversely, only a part is made to react, and it is contained. The epoxy group in the structure of the fluorine (meth) acryl-modified organosilicon compound may remain. Moreover, in the case of reaction, it reacts by making compound (B) equivalence or excess with respect to all the epoxy groups contained in compound (A), and it stops, when reaction reaches the target reaction rate. Techniques can also be used. In particular, it is preferable to use 0.5 to 2.0 equivalents, particularly 0.8 to 1.1 equivalents of the compound (B) with respect to 1 equivalent of the epoxy group of the compound (A).
この反応は、通常、５０〜１５０℃の範囲の温度で１〜５０時間程度で行う。このとき必要に応じて反応を促進するために触媒を用いることもできる。このような触媒としては、例えば、トリフェニルホスフィン等のホスフィン類、トリエチルアミン、ジメチルブチルアミン、トリ−ｎ−ブチルアミン等のアミン類、テトラメチルアンモニウム塩、テトラエチルアンモニウム塩、テトラブチルアンモニウム塩、ベンジルトリエチルアンモニウム塩等の第四級塩、又は第四級ホスホニウム塩、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、塩化リチウム、臭化リチウム、塩化第一錫、塩化亜鉛等の金属ハロゲン化物を挙げることができるが、特にホスフィン類が好適である。 This reaction is usually carried out at a temperature in the range of 50 to 150 ° C. for about 1 to 50 hours. At this time, if necessary, a catalyst may be used to promote the reaction. Examples of such catalysts include phosphines such as triphenylphosphine, amines such as triethylamine, dimethylbutylamine, and tri-n-butylamine, tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt, and benzyltriethylammonium salt. Quaternary salts such as, quaternary phosphonium salts, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, metal halogens such as lithium chloride, lithium bromide, stannous chloride, zinc chloride Among them, phosphines are particularly preferable.
また、反応の際には反応中の重合やこれにともなうゲル化を防ぐため、エアレーション等の空気（酸素）の導入による措置やメチルハイドロキノン、ハイドロキノン等のハイドロキノン類、２，６−ジ−ｔ−ブチル−４−メチルフェノール等のヒンダートフェノール類、ｐ−ベンゾキノン、ｐ−トルキノン等のベンゾキノン類、フェノチアジン等の公知の重合禁止剤を用いることができる。 In the reaction, in order to prevent polymerization during the reaction and gelation associated therewith, measures by introducing air (oxygen) such as aeration, hydroquinones such as methylhydroquinone and hydroquinone, 2,6-di-t- Known hindered phenols such as butyl-4-methylphenol, benzoquinones such as p-benzoquinone and p-toluquinone, and known polymerization inhibitors such as phenothiazine can be used.
更に反応を円滑に行うために反応系を溶媒で希釈することもできる。溶媒としては任意のものを用いることができるが、化合物（Ａ）、（Ｂ）及び反応に伴い発生する水酸基、エステル基と不活性な溶媒であることが望ましい。具体的にはテトラヒドロフラン、ジエチレングリコールジメチルエーテル等のエーテル類、トルエン、キシレン等の芳香族系炭化水素溶媒、酢酸エチル、酢酸ブチル等の飽和脂肪族エステル類、ベンゾトリフロライド、ｍ−キシレンヘキサフロライド、あるいはアサヒクリン（旭硝子（株）製）、ノベックＨＦＥ（住友スリーエム（株）製）等、各社から市販されているフッ素化溶媒を用いることもできる。これらの溶媒は、１種単独で又は２種以上の混合で使用することもできる。
このようにして合成することのできる本発明の化合物として、例えば以下のものを例示できる。
Further, the reaction system can be diluted with a solvent in order to carry out the reaction smoothly. Although any solvent can be used, it is desirable that the solvent be inert with the compounds (A) and (B) and the hydroxyl group and ester group generated during the reaction. Specifically, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, aromatic hydrocarbon solvents such as toluene and xylene, saturated aliphatic esters such as ethyl acetate and butyl acetate, benzotrifluoride, m-xylene hexafluoride, Alternatively, fluorinated solvents commercially available from various companies such as Asahiklin (manufactured by Asahi Glass Co., Ltd.) and Novec HFE (manufactured by Sumitomo 3M Co., Ltd.) can also be used. These solvents can be used alone or in a mixture of two or more.
Examples of the compound of the present invention that can be synthesized in this manner include the following.
以上のようにして得られる本発明の含フッ素（メタ）アクリル変性有機ケイ素化合物は、非フッ素系の硬化性組成物に配合し、硬化物表面に防汚性、耐指紋性、撥水性、撥油性を付与する硬化性組成物を提供することができる。非フッ素系硬化性組成物の有効成分１００質量部に対する含フッ素（メタ）アクリル変性有機ケイ素化合物の配合量は、０．００５〜２０質量部であり、好ましくは０．０１〜１０質量部である。上記の上限値を超える値では添加した含フッ素（メタ）アクリル変性有機ケイ素化合物成分層が厚くなる場合があり、硬化物としての性能を損なう可能性があり、下限値未満ではハードコート層の表面を十分に覆うことができなくなる場合がある。 The fluorine-containing (meth) acryl-modified organosilicon compound of the present invention obtained as described above is blended in a non-fluorine-based curable composition, and the cured product surface has antifouling properties, fingerprint resistance, water repellency, and water repellency. A curable composition imparting oiliness can be provided. The compounding amount of the fluorine-containing (meth) acryl-modified organosilicon compound with respect to 100 parts by mass of the active ingredient of the non-fluorinated curable composition is 0.005 to 20 parts by mass, preferably 0.01 to 10 parts by mass. . If the value exceeds the above upper limit value, the added fluorine-containing (meth) acryl-modified organosilicon compound component layer may become thick, which may impair the performance as a cured product, and if it is less than the lower limit value, the surface of the hard coat layer May not be sufficiently covered.
非フッ素系の硬化性組成物としては、本発明の化合物と混合、硬化可能であれば、いかなるものであっても使用することができるが、特に紫外線及び電子線等の活性エネルギー線硬化型樹脂が好適である。
このような活性エネルギー線硬化型樹脂としては、既存のいかなるものも用いることができ、特に制限されるものではないが、特に（メタ）アクリル化合物類を含む硬化性組成物が好適である。このような（メタ）アクリル化合物としては１〜６官能の（メタ）アクリル化合物モノマー類の他に、例えばポリエーテルポリオールやポリエステルポリオールとポリイソシアネートの反応によって得られるポリウレタンオリゴマーを、（メタ）アクリル酸との反応でエステル化することにより得られるウレタンアクリレート類、多価カルボン酸と多価アルコールの縮合によって得られる両末端に水酸基を有するポリエステルオリゴマーの水酸基を（メタ）アクリル酸でエステル化すること又は多価カルボン酸にアルキレンオキシドを付加して得られるオリゴマーの末端の水酸基を（メタ）アクリル酸でエステル化することにより得られるポリエステルアクリレート類、比較的低分子量のビスフェノール型エポキシ樹脂やノボラックエポキシ樹脂やその他脂肪族エポキシ樹脂等のオキシラン環と、（メタ）アクリル酸との反応でエステル化することにより得ることができるエポキシアクリレート類等、オリゴマー、ポリマー変性成分を含むものが特に好適である。
Any non-fluorine-based curable composition can be used as long as it can be mixed and cured with the compound of the present invention. In particular, active energy ray-curable resins such as ultraviolet rays and electron beams are usable. Is preferred.
As such an active energy ray-curable resin, any existing one can be used and is not particularly limited, but a curable composition containing (meth) acryl compounds is particularly suitable. As such (meth) acrylic compounds, in addition to 1-6 functional (meth) acrylic compound monomers, for example, polyurethane oligomers obtained by reaction of polyether polyols or polyester polyols with polyisocyanates, (meth) acrylic acid Esterify the hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of urethane acrylates, polyvalent carboxylic acids and polyhydric alcohols obtained by esterification with (meth) acrylic acid, or Polyester acrylates obtained by esterifying hydroxyl groups at the end of oligomers obtained by adding alkylene oxides to polycarboxylic acids with (meth) acrylic acid, relatively low molecular weight bisphenol type epoxy resins and novolac epoxies And oxirane ring, such as butter and other aliphatic epoxy resin, (meth) epoxy acrylates can be obtained by esterification reaction of acrylic acid or the like, oligomer, those containing polymeric modifying component is particularly preferred.
これら活性エネルギー線硬化型樹脂の具体的な例としては、主剤として１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキシド変性ジ（メタ）アクリレート、イソシアヌル酸ＥＯ変性トリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、グリセロールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、フタル酸水素−（２，２，２−トリ−（メタ）アクリロイルオキシメチル）エチル、グリセロールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ソルビトールヘキサ（メタ）アクリレート等の２〜６官能の（メタ）アクリル化合物、これらの（メタ）アクリル化合物をエチレンオキシド、プロピレンオキシド、エピクロルヒドリン、脂肪酸、アルキル、ウレタン変性品、エポキシ樹脂にアクリル酸を付加させて得られるエポキシアクリレート類、アクリル酸エステル共重合体の側鎖に（メタ）アクリロイル基を導入した共重合体等を含むものが挙げられる。 Specific examples of these active energy ray-curable resins include 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and isocyanuric acid ethylene oxide modified as the main agent. Di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, Hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylo 2-6 functional (meth) acrylic compounds such as rupropanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, these (meth) Introduced (meth) acryloyl group into the side chain of acrylic acid copolymer with ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl, urethane modified products, epoxy acrylates obtained by adding acrylic acid to epoxy resin And those containing the above-mentioned copolymer.
このような活性エネルギー線で硬化可能な硬化性組成物は、ハードコート剤としてあるいは活性エネルギー線硬化型インク等として各社からさまざまなものが市販されている。例えば、荒川化学工業（株）「ビームセット」、大橋化学工業（株）「ユービック」、オリジン電気（株）「ＵＶコート」、カシュー（株）「カシューＵＶ」、ＪＳＲ（株）「デソライト」、大日精化工業（株）「セイカビーム」、日本合成化学（株）「紫光」、藤倉化成（株）「フジハード」、三菱レイヨン（株）「ダイヤビーム」、武蔵塗料（株）「ウルトラバイン」、十条ケミカル（株）「レイキュアー」等の商品名が挙げられる。また、本発明の化合物は、フッ素系のハードコード組成物に配合することによって、撥水性、撥油性等を更に増強することもできる。 Various curable compositions curable with active energy rays are commercially available from various companies as hard coating agents or active energy ray curable inks. For example, Arakawa Chemical Industry Co., Ltd. “Beam Set”, Ohashi Chemical Industry Co., Ltd. “Uvic”, Origin Electric Co., Ltd. “UV Coat”, Cashew Co., Ltd. “Cashew UV”, JSR Co., Ltd. “Desolite” Dainichi Seika Kogyo Co., Ltd. “Seika Beam”, Nippon Synthetic Chemical Co., Ltd. “Shiko”, Fujikura Kasei Co., Ltd. “Fujihardt”, Mitsubishi Rayon Co., Ltd. “Diabeam”, Musashi Paint Co., Ltd. “Ultra Vine”, Trade names such as “Jujo Chemical Co., Ltd.“ Reicure ”are listed. In addition, the compound of the present invention can further enhance water repellency, oil repellency and the like by blending with a fluorine-based hard cord composition.
また、硬化性組成物中には、エポキシ基及び／又は水酸基との反応可能な化合物を配合し、例えば加熱と活性エネルギー線の複合硬化型の組成物とすることもできる。エポキシ基及び／又は水酸基との反応可能な化合物としては、多官能アミノ化合物、多官能カルボン酸化合物、不飽和カルボン酸類、酸無水物、多官能アルコール類、多官能シラノール化合物、エポキシ化合物、多官能イソシアネート化合物等が挙げられ、特に多官能エポキシ化合物、多官能イソシアネート化合物が好適である。 Moreover, the compound which can react with an epoxy group and / or a hydroxyl group is mix | blended in a curable composition, for example, it can also be set as the composite curable composition of a heating and an active energy ray. As a compound capable of reacting with an epoxy group and / or a hydroxyl group, a polyfunctional amino compound, a polyfunctional carboxylic acid compound, an unsaturated carboxylic acid, an acid anhydride, a polyfunctional alcohol, a polyfunctional silanol compound, an epoxy compound, a polyfunctional An isocyanate compound etc. are mentioned, Especially a polyfunctional epoxy compound and a polyfunctional isocyanate compound are suitable.
このようなエポキシ化合物としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ化合物、脂環式エポキシ化合物、グリシジルエステル型エポキシ化合物、グリシジルアミン型エポキシ化合物、ヒダントイン型エポキシ化合物、イソシアヌレート型エポキシ化合物、レゾルシン型エポキシ化合物、及びそれらのハロゲン化物、水素添加物、及びグリシジル（メタ）アクリレート重合体やグリシジル（メタ）アクリレートとエポキシ基を持たない各種（メタ）アクリレート類と共重合体等が例示できる。 Examples of such epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy compounds. Compounds, alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, hydantoin type epoxy compounds, isocyanurate type epoxy compounds, resorcin type epoxy compounds, and their halides, hydrogenated products, and glycidyl (meta ) Acrylate polymers, glycidyl (meth) acrylates, various (meth) acrylates having no epoxy group, copolymers, and the like.
また多官能イソシアネート化合物としては、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、１，３−キシレンジイソシアネート、１，４−キシレンジイソシアネート、キシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、ジフェニルメタンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジベンジルジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、あるいは水添キシリレンジイソシアネート、水添ジフェニルメタンジイソシアネート等の芳香族ジイソシアネート化合物の水添化物、トリフェニルメタントリイソシアネート、ジメチレントリフェニルトリイソシアネート等のような二価又は三価のジイソシアネート化合物、あるいはポリイソシアネート化合物や、これらを多量化させて得られる多量化ポリイソシアネート化合物等のイソシアネート基含有化合物が挙げられる。更に２官能イソシアネートと１分子に２個以上の水酸基を有する多官能アルコール類を反応させた多官能イソシアネート化合物が例示できる。
これらエポキシ基及び／又は水酸基との反応可能な化合物は１種類でも２種類以上の複数でも配合可能である。
Examples of the polyfunctional isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m -Phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, or hydrogenated xylylene diisocyanate, Hydrogenated aromatic diisocyanate compounds such as hydrogenated diphenylmethane diisocyanate, divalent or trivalent diisocyanate compounds such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, etc., or polyisocyanate compounds And an isocyanate group-containing compound such as a multimerized polyisocyanate compound. Furthermore, a polyfunctional isocyanate compound obtained by reacting a bifunctional isocyanate and a polyfunctional alcohol having two or more hydroxyl groups per molecule can be exemplified.
These compounds capable of reacting with an epoxy group and / or a hydroxyl group can be used alone or in combination of two or more.
以上のような本発明の化合物を含む硬化性組成物には、必要に応じて種々の添加剤を配合することができる。このような添加剤としては、例えば、光重合開始剤、熱重合開始剤、重合促進剤、エポキシ硬化触媒、フィラー、染顔料、レベリング剤、希釈剤、非反応性高分子樹脂、シランカップリング剤、酸化防止剤、紫外線吸収剤、光安定剤、消泡剤、分散剤、チクソトロピー性付与剤等が挙げられる。 Various additives can be blended in the curable composition containing the compound of the present invention as described above, if necessary. Examples of such additives include photopolymerization initiators, thermal polymerization initiators, polymerization accelerators, epoxy curing catalysts, fillers, dyes and pigments, leveling agents, diluents, non-reactive polymer resins, and silane coupling agents. , Antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, dispersants, thixotropic agents and the like.
本発明の化合物は、硬化性組成物に配合することで、硬化物表面に防汚、撥水、撥油性、耐指紋性を付与するのに有用である。これによって、指紋、皮脂、汗等の人脂、化粧品等により汚れ難くなり、汚れが付着した場合であっても拭き取り性に優れた硬化物表面を与える。このため、本発明の化合物は、人体が触れて人脂、化粧品等により汚される可能性のある物品の表面に施与される塗装膜もしくは保護膜を形成するために使用されるハードコート組成物の添加剤として特に有用である。このようなハードコート処理される物品としては、例えば、光磁気ディスク、ＣＤ・ＬＤ・ＤＶＤ・ブルーレイディスク等の光ディスク、ホログラム記録等に代表される光記録媒体；メガネレンズ、プリズム、レンズシート、ペリクル膜、偏光板、光学フィルター、レンチキュラーレンズ、フレネルレンズ、反射防止膜、光ファイバーや光カプラー等の光学部品・光デバイス；ＣＲＴ、液晶ディスプレイ、プラズマディスプレイ、エレクトロルミネッセンスディスプレイ、背面投写型ディスプレイ、蛍光表示管（ＶＦＤ）、フィールドエミッションプロジェクションディスプレイ、トナー系ディスプレイ等の各種画面表示機器；特にＰＣ、携帯電話、携帯情報端末、ゲーム機、電子ブックリーダー、デジタルカメラ、デジタルビデオカメラ、自動現金引出し預け入れ装置、現金自動支払機、自動販売機、自動車用等のナビゲーション装置、セキュリティーシステム端末等の画像表示装置、及びその操作も行うタッチパネル（タッチセンサー、タッチスクリーン）式画像表示入力装置；携帯電話、携帯情報端末、電子ブックリーダー、携帯音楽プレイヤー、携帯ゲーム機、リモートコントローラ、コントローラ、キーボード等、車載装置用パネルスイッチなどの入力装置；携帯電話、携帯情報端末、カメラ、携帯音楽プレイヤー、携帯ゲーム機等の筐体表面；自動車の外装、ピアノ、高級家具、大理石等の塗装及び表面；美術品展示用保護ガラス、ショーウインドー、ショーケース、広告用カバー、フォトスタンド用のカバー、腕時計、自動車用フロントガラス、列車、航空機等の窓ガラス、自動車ヘッドライト、テールランプ等の透明なガラス製又は透明なプラスチック製（アクリル、ポリカーボネート等）部材；各種ミラー部材等が挙げられる。これら用途において、本発明の化合物を配合したハードコート組成物は、ただ単に目的物の表面への塗工によるものだけでなく、インモールド成形等で広く用いられている転写型ハードコートにも使用することができる。 The compound of the present invention is useful for imparting antifouling, water repellency, oil repellency, and fingerprint resistance to the surface of a cured product by blending with the curable composition. As a result, it becomes difficult to be soiled by human fats such as fingerprints, sebum, sweat, cosmetics, and the like, and a cured product surface excellent in wiping property is provided even when the soil adheres. Therefore, the compound of the present invention is a hard coat composition used to form a coating film or a protective film applied to the surface of an article that may be touched by the human body and contaminated by human fat, cosmetics, etc. It is particularly useful as an additive. Examples of such an article to be hard-coated include magneto-optical disks, optical disks such as CD / LD / DVD / Blu-ray disks, optical recording media represented by hologram recording, etc .; eyeglass lenses, prisms, lens sheets, pellicles Optical parts and optical devices such as films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, antireflection films, optical fibers and optical couplers; CRTs, liquid crystal displays, plasma displays, electroluminescence displays, rear projection displays, fluorescent display tubes (VFD), field emission projection display, various screen display devices such as toner-based display; in particular, PC, mobile phone, portable information terminal, game machine, electronic book reader, digital camera, digital video camera, Dynamic cash deposit / deposit device, cash dispenser, vending machine, navigation device for automobiles, image display device such as security system terminal, and touch panel (touch sensor, touch screen) type image display input device for operation thereof; Input devices such as mobile phones, portable information terminals, electronic book readers, portable music players, portable game machines, remote controllers, controllers, keyboards, panel switches for in-vehicle devices; cellular phones, portable information terminals, cameras, portable music players, Housing surface of portable game machines, etc .; Painting and surfaces of automobile exteriors, pianos, luxury furniture, marble, etc .; protective glass for art exhibits, show windows, showcases, advertising covers, photo stand covers, watches, automobiles Windshield, train, aircraft window Las, automobile headlights, made of transparent glass of the tail lamp and the like or a transparent plastic (acrylic, polycarbonate, etc.) member; various mirror member, and the like. In these applications, the hard coat composition containing the compound of the present invention is not only applied to the surface of the object, but also used for transfer type hard coats widely used in in-mold molding and the like. can do.
また、本発明のパーフルオロポリエーテル基等を有する（メタ）アクリル変性有機ケイ素化合物は、紫外線硬化型レジスト液に添加し、露光を行うことで、硬化後のレジスト表面とレジストが除去された部分の撥液性に大きな差を付けることが可能であり、レジスト樹脂表面への現像液や液晶溶液の残存、汚染を防ぐことができる。 In addition, the (meth) acryl-modified organosilicon compound having a perfluoropolyether group or the like of the present invention is added to an ultraviolet curable resist solution and exposed to light, so that the cured resist surface and the resist are removed. It is possible to make a large difference in the liquid repellency, and it is possible to prevent the developer and liquid crystal solution from remaining on the resist resin surface and contamination.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［実施例１］
乾燥窒素雰囲気下で、還流装置と攪拌装置を備えた２，０００ｍＬ三口フラスコに、下記式（１２）で示される両末端にα−不飽和結合を有するパーフルオロポリエーテル５００ｇと、ｍ−キシレンヘキサフロライド７００ｇ、及びテトラメチルシクロテトラシロキサン３６１ｇを投入し、攪拌しながら９０℃まで加熱した。ここに白金／１，３−ジビニル−テトラメチルジシロキサン錯体のトルエン溶液０．４４２ｇ（Ｐｔ単体として１．１×１０-6モルを含有）を仕込み、内温を９０℃以上に維持したまま４時間攪拌を継続した。
1Ｈ−ＮＭＲで原料のアリル基が消失したのを確認した後、溶剤や過剰のテトラメチルシクロテトラシロキサンを減圧溜去し、活性炭処理を行い、下記式（１３）で示す無色透明の液体であるパーフルオロポリエーテル含有化合物（化合物Ｉ）４９８ｇを得た。
ＣＨ2＝ＣＨ−ＣＨ2−Ｏ−ＣＨ2−Ｒｆ1−ＣＨ2−Ｏ−ＣＨ2−ＣＨ＝ＣＨ2 （１２）
Ｒｆ1：−ＣＦ2（ＯＣＦ2 ＣＦ2）p（ＯＣＦ2）qＯＣＦ2− （以下、同じ。）
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５）
[Example 1]
Under a dry nitrogen atmosphere, in a 2,000 mL three-necked flask equipped with a reflux device and a stirring device, 500 g of perfluoropolyether having α-unsaturated bonds at both ends represented by the following formula (12), and m-xylene hexa 700 g of fluoride and 361 g of tetramethylcyclotetrasiloxane were added and heated to 90 ° C. with stirring. Here, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 −6 mol as a simple substance of Pt) was added, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for an hour.
After confirming the disappearance of the allyl group of the raw material by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure and treated with activated carbon to obtain a colorless and transparent liquid represented by the following formula (13). 498 g of a certain perfluoropolyether-containing compound (Compound I) was obtained.
CH 2 = CH-CH 2 -O -CH 2 -Rf 1 -CH 2 -O-CH 2 -CH = CH 2 (12)
Rf 1 : —CF 2 (OCF 2 CF 2 ) p (OCF 2 ) q OCF 2 — (hereinafter the same)
(P / q = 0.9, p + q≈45)
化合物（Ｉ）６０．０ｇに対して、アリルグリシジルエーテル１０．０ｇ、ｍ−キシレンヘキサフロライド６０．０ｇを混合し、攪拌しながら窒素雰囲気下で８０℃に加熱した。ここに白金／１，３−ジビニル−テトラメチルジシロキサン錯体のトルエン溶液０．０２２１ｇ（Ｐｔ単体として５．６×１０-8モルを含有）を投入し、内温を９０〜１２０℃に維持したまま６時間攪拌を継続した。1Ｈ−ＮＭＲで原料のＳｉ−Ｈが消失したのを確認した後、活性炭処理を行い、溶剤や過剰のアリルグリシジルエーテルを減圧溜去し、下記式（１４）で示される化合物（ＩＩ）６６.２ｇを得た。 To 60.0 g of compound (I), 10.0 g of allyl glycidyl ether and 60.0 g of m-xylene hexafluoride were mixed and heated to 80 ° C. in a nitrogen atmosphere with stirring. 0.0221 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 5.6 × 10 −8 mol as a simple substance of Pt) was added thereto, and the internal temperature was maintained at 90 to 120 ° C. Stirring was continued for 6 hours. After confirming the disappearance of the raw material Si-H by 1 H-NMR, the activated carbon treatment was carried out, and the solvent and excess allyl glycidyl ether were distilled off under reduced pressure to obtain the compound (II) 66 represented by the following formula (14). 0.2 g was obtained.
化合物（ＩＩ）６０．０ｇ、酢酸ブチル６０．０ｇ、アクリル酸５．５０ｇ、トリフェニルホスフィン０．１２ｇ、ｐ−メトキシフェノール０．０８ｇを混合し空気によるバブリングと攪拌を行いながら、１１０℃まで加熱し、８時間反応させた。反応後、活性炭による吸着処理を行った後に溶剤と未反応のアクリル酸を減圧溜去し、得られたサンプルの1Ｈ−ＮＭＲから、平均して下記式（１５）又は（１６）で表される構造を有する化合物（ＩＩＩ）６２ｇを得た。 Compound (II) 60.0 g, butyl acetate 60.0 g, acrylic acid 5.50 g, triphenylphosphine 0.12 g, p-methoxyphenol 0.08 g were mixed and heated to 110 ° C. while bubbling with air and stirring. And allowed to react for 8 hours. After the reaction, after adsorption treatment with activated carbon, the solvent and unreacted acrylic acid were distilled off under reduced pressure. From the 1 H-NMR of the obtained sample, it was represented by the following formula (15) or (16) on average. 62 g of compound (III) having the following structure was obtained.
1Ｈ−ＮＭＲスペクトルのケミカルシフトを表１に示す（測定装置：Ｂｒｕｋｅｒ製 ＡＶＡＮＣＥ４００、溶媒ＣＤＣｌ3）。
The chemical shift of the 1 H-NMR spectrum is shown in Table 1 (measuring device: AVANCE 400 manufactured by Bruker, solvent CDCl 3 ).
［実施例２］
乾燥窒素雰囲気下で、還流装置と攪拌装置を備えた１００ｍＬ三口フラスコに下記式（１７）
In a dry nitrogen atmosphere, a 100 mL three-necked flask equipped with a reflux device and a stirrer has the following formula (17)
得られた化合物（ＩＶ）３３．０ｇに対してアクリル酸５．１ｇ、トリフェニルホスフィン０．１１ｇ、ｐ−メトキシフェノール０．０６ｇを混合し空気によるバブリングと攪拌を行いながら、１１０℃まで加熱し、１０時間反応させた。反応後、活性炭による吸着処理を行った後に溶剤と未反応のアクリル酸を減圧溜去し、得られたサンプルの1Ｈ−ＮＭＲから、下記式（１９）で表される構造を有する化合物（Ｖ）３５．２ｇを得た。
1Ｈ−ＮＭＲスペクトルのケミカルシフトを表２に示す（測定装置：Ｂｒｕｋｅｒ製 ＡＶＡＮＣＥ４００、溶媒ＣＤＣｌ3）。
The resulting compound (IV) (33.0 g) was mixed with 5.1 g of acrylic acid, 0.11 g of triphenylphosphine and 0.06 g of p-methoxyphenol and heated to 110 ° C. while bubbling and stirring with air. The reaction was allowed for 10 hours. After the reaction, after adsorption treatment with activated carbon, the solvent and unreacted acrylic acid were distilled off under reduced pressure. From 1 H-NMR of the obtained sample, a compound having a structure represented by the following formula (19) (V ) 35.2 g was obtained.
The chemical shift of the 1 H-NMR spectrum is shown in Table 2 (measuring device: AVANCE 400 manufactured by Bruker, solvent CDCl 3 ).
［比較例１］
乾燥空気存在下で、還流装置とメカニカルスターラーを備えた２００ｍＬ三口フラスコ中に２−イソシアネートエチルメタクリレート１５．５ｇとジオクチル錫ラウレート０．００５ｇを仕込み、パーフルオロポリエーテルジオール（ソルベイ・ソレクシス社製、商品名、ＦＯＭＢＬＩＮ Ｄ２０００、平均分子量２，０００）１００ｇを５０℃で１時間かけて滴下した。滴下終了後５０℃で５時間攪拌した。反応物のＩＲスペクトルからは２，３００ｃｍ-1に現れる−Ｎ＝Ｃ＝Ｏ基由来のピークが消失しており、両末端にメタクリル基を有するパーフルオロポリエーテルジオールが得られた。
[Comparative Example 1]
In the presence of dry air, 15.5 g of 2-isocyanatoethyl methacrylate and 0.005 g of dioctyltin laurate were charged into a 200 mL three-necked flask equipped with a reflux apparatus and a mechanical stirrer, and perfluoropolyether diol (product of Solvay Solexis, product) Name, FOMBLIN D2000, average molecular weight 2,000) 100 g was added dropwise at 50 ° C. over 1 hour. After completion of dropping, the mixture was stirred at 50 ° C. for 5 hours. From the IR spectrum of the reaction product, a peak derived from —N═C═O group appearing at 2,300 cm −1 disappeared, and a perfluoropolyether diol having a methacryl group at both ends was obtained.
実施例１、２及び比較例１の化合物各０．５ｇを、下記の各種溶媒１０ｇと混合し、その溶解性を目視にて調べた結果を表３に示す。表３において、○は透明な溶液になったことを、×はそれ以外（沈殿、分離及び濁りのいずれかが発生した状態）であったことを示す。 Table 3 shows the results obtained by mixing 0.5 g of each of the compounds of Examples 1 and 2 and Comparative Example 1 with 10 g of the following various solvents and visually examining the solubility thereof. In Table 3, ◯ indicates that the solution became a transparent solution, and X indicates that it was otherwise (a state in which any of precipitation, separation, and turbidity occurred).
ＨＦＣＦ−２２５：ジクロロペンタフルオロプロパン
表３に示すように、実施例１、２の化合物は、従来の含フッ素（メタ）アクリル化合物に比べて、多くの非フッ素化溶媒に溶解する。 As shown in Table 3, the compounds of Examples 1 and 2 are soluble in many non-fluorinated solvents as compared with conventional fluorine-containing (meth) acrylic compounds.
硬化性組成物における評価１
実施例１、２で調製した化合物をそれぞれ以下の組成で配合した溶液を調製した。なお、ブランクとして、何も添加剤を含まない溶液も調製した。
Evaluation 1 in curable composition
Solutions prepared by blending the compounds prepared in Examples 1 and 2 with the following compositions were prepared. As a blank, a solution containing no additive was also prepared.
各溶液をガラス板上にスピンコートし、コンベア型紫外線照射装置において１．６Ｊ／ｃｍ2の紫外線を照射して硬化膜を形成し、その外観を目視により評価した。また、接触角計（協和界面科学（株）製）を用いて、水接触角、オレイン酸接触角を測定した。なお、比較例の化合物は、溶解性が悪く溶液にならなかったため、ハードコートを作ることができなかった。
表５に、それぞれのハードコート処理表面の特性を示す。マジックはじき性は、ゼブラ（株）製油性マーカー、ハイマッキーで、表面に線を引いた場合の、インキのはじかれ具合を目視で評価した。指紋拭取り性は、表面に人差し指を押し当てて指紋を付着させた後にティッシュペーパーで拭きその拭きとり性を目視で評価した。結果を以下に示す。
Each solution was spin-coated on a glass plate, and a cured film was formed by irradiating with 1.6 J / cm 2 ultraviolet rays in a conveyor type ultraviolet irradiation device, and the appearance was visually evaluated. Moreover, the water contact angle and the oleic acid contact angle were measured using the contact angle meter (made by Kyowa Interface Science Co., Ltd.). In addition, since the compound of the comparative example had poor solubility and did not become a solution, a hard coat could not be made.
Table 5 shows the characteristics of each hard coat treated surface. The magic repellency was visually evaluated by repelling the ink when a line was drawn on the surface using an oil-based marker, Himackey, manufactured by Zebra Corporation. The fingerprint wiping property was evaluated by visually wiping with a tissue paper after pressing the index finger against the surface to attach the fingerprint. The results are shown below.
ハードコート組成物における評価２
実施例１、２の化合物を以下の組成で配合した溶液を調製した。なお、ブランクとして、添加剤を含まない溶液も調製した。
Evaluation 2 in hard coat composition
A solution was prepared by blending the compounds of Examples 1 and 2 with the following composition. In addition, the solution which does not contain an additive was also prepared as a blank.
各溶液をガラス板上にスピンコートし、コンベア型紫外線照射装置において窒素雰囲気中で１．６Ｊ／ｃｍ2の紫外線を照射して、硬化膜を形成し、その外観を目視により評価した。また、接触角計（協和界面科学（株）製）を用いて、水接触角、オレイン酸接触角を測定した。なお、比較例の化合物は、溶解性が悪く溶液にならなかった。
表７に、それぞれのハードコート処理表面を評価１と同様の方法で評価した結果を示す。
Each solution was spin-coated on a glass plate, irradiated with 1.6 J / cm 2 of ultraviolet light in a nitrogen atmosphere in a conveyor type ultraviolet irradiation device to form a cured film, and the appearance was visually evaluated. Moreover, the water contact angle and the oleic acid contact angle were measured using the contact angle meter (made by Kyowa Interface Science Co., Ltd.). In addition, the compound of the comparative example had poor solubility and did not form a solution.
Table 7 shows the results of evaluating each hard coat-treated surface in the same manner as in Evaluation 1.
Claims (6)
で表される含フッ素エポキシ変性有機ケイ素化合物に、（Ｂ）（メタ）アクリル基を有する不飽和モノカルボン酸を付加反応させることにより得られた含フッ素（メタ）アクリル変性有機ケイ素化合物。 (A) The following general formula (1)
(B) A fluorine-containing (meth) acryl-modified organosilicon compound obtained by subjecting an unsaturated monocarboxylic acid having a (meth) acryl group to an addition reaction to a fluorine-containing epoxy-modified organosilicon compound represented by the formula:
−ＣiＦ2iＯ−
（ｉは、単位毎に独立に、１〜６の整数である。）
で表される繰り返し単位を１〜５００個含むことを特徴とする請求項１記載の化合物。 In the general formula (1), Rf represents the following formula -C i F 2i O-
(I is an integer of 1 to 6 independently for each unit.)
The compound according to claim 1, comprising 1 to 500 repeating units represented by the formula:
で示される基と結合する。また、２種類の繰り返し単位の並びはランダムである。Ｒｆは式（１）で定義した通りである。）
で表される請求項１又は２記載の化合物。 In the general formula (1), Q 1 represents the following formula (2)
It bonds with the group shown by. Also, the arrangement of the two types of repeating units is random. Rf is as defined in Formula (1). )
The compound of Claim 1 or 2 represented by these.
−［Ｑ3−Ｒｆ’−Ｑ3−Ｔ］v−Ｑf−Ｒｆ’−Ｑ3− （３）
（但し、Ｒｆ’は二価の分子量３００〜３０，０００のパーフルオロポリエーテル基であり、途中分岐を含んでいても良い。Ｑ3は二価の有機基であり、酸素原子、窒素原子、フッ素原子又はケイ素原子を含んでいてもよく、また、環状構造又は不飽和結合を有する基であってもよい。ＱfはＱ3又はフッ素原子である。Ｔは、下記式（４）
で表される連結基であり、ｖは０〜５の整数であり、なおかつＱfがフッ素原子のときｖ＝０である。）
で表される請求項１〜３のいずれか１項記載の化合物。 In general formula (1), Rf is the following general formula (3)
− [Q 3 −Rf′−Q 3 −T] v −Q f −Rf′−Q 3 − (3)
(However, Rf ′ is a divalent perfluoropolyether group having a molecular weight of 300 to 30,000, and may contain a branch in the middle. Q 3 is a divalent organic group, and includes an oxygen atom, a nitrogen atom, It may contain a fluorine atom or a silicon atom, and may be a group having a cyclic structure or an unsaturated bond, Q f is Q 3 or a fluorine atom, T is the following formula (4)
Wherein v is an integer of 0 to 5 and v = 0 when Q f is a fluorine atom. )
The compound of any one of Claims 1-3 represented by these.
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5477160B2 (en) | 2014-04-23 |
| TW201213340A (en) | 2012-04-01 |
| KR101841648B1 (en) | 2018-05-04 |
| CN102382291A (en) | 2012-03-21 |
| CN102382291B (en) | 2015-06-10 |
| TWI510499B (en) | 2015-12-01 |
| KR20110128140A (en) | 2011-11-28 |
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