JP7255666B2 - Fluorine-containing curable composition and article - Google Patents
Fluorine-containing curable composition and article Download PDFInfo
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- JP7255666B2 JP7255666B2 JP2021501730A JP2021501730A JP7255666B2 JP 7255666 B2 JP7255666 B2 JP 7255666B2 JP 2021501730 A JP2021501730 A JP 2021501730A JP 2021501730 A JP2021501730 A JP 2021501730A JP 7255666 B2 JP7255666 B2 JP 7255666B2
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- fluorine
- meth
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- 229910052731 fluorine Inorganic materials 0.000 title claims description 170
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 165
- 239000011737 fluorine Substances 0.000 title claims description 165
- 239000000203 mixture Substances 0.000 title claims description 104
- -1 fluorinated acrylic compound Chemical class 0.000 claims description 181
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 91
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 73
- 150000001875 compounds Chemical class 0.000 claims description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 12
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 10
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 8
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010702 perfluoropolyether Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 5
- 238000006243 chemical reaction Methods 0.000 description 63
- 239000010408 film Substances 0.000 description 41
- 239000002904 solvent Substances 0.000 description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 33
- 238000000576 coating method Methods 0.000 description 30
- 239000010410 layer Substances 0.000 description 26
- 239000012948 isocyanate Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 230000003373 anti-fouling effect Effects 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 15
- 238000001723 curing Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 11
- 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 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 239000000370 acceptor Substances 0.000 description 8
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- 239000000243 solution Substances 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 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 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000005642 Oleic acid Substances 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000004210 ether based solvent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 4
- 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 4
- 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 4
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 4
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- 229940093858 ethyl acetoacetate Drugs 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
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- 238000010992 reflux Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
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- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 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 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 3
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
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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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
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- 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
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/18—Esters containing halogen
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- 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
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/22—Esters containing nitrogen
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- 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
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
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Description
本発明は、防汚性、滑り性に優れた含フッ素硬化性組成物、及び該組成物の硬化被膜を表面に有する物品に関する。 TECHNICAL FIELD The present invention relates to a fluorine-containing curable composition excellent in antifouling properties and slipperiness, and an article having a cured film of the composition on its surface.
従来、樹脂成形体等の表面を保護する手段として、ハードコート処理が広く一般に用いられている。これは成形体の表面に硬質の硬化樹脂層(ハードコート層)を形成し、傷つき難くするものである。ハードコート層を構成する材料としては、熱硬化性樹脂や紫外線もしくは電子線硬化型樹脂など活性エネルギー線による硬化性組成物が多く使用されている。 2. Description of the Related Art Conventionally, hard coating treatment has been widely used as means for protecting the surface of resin moldings and the like. This forms a hard cured resin layer (hard coat layer) on the surface of the molded article to make it difficult to be damaged. As a material for forming the hard coat layer, a composition curable by active energy rays such as a thermosetting resin, an ultraviolet curable resin, or an electron beam curable resin is often used.
一方、樹脂成形品の利用分野の拡大や高付加価値化の流れに伴い、硬化樹脂層(ハードコート層)に対する高機能化の要望が高まっており、その一つとして、ハードコート層への防汚性の付与が求められている。これはハードコート層の表面に撥水性、撥油性などの性質を付与することにより、汚れ難く、あるいは汚れても容易に取り除くことができるようにするものである。 On the other hand, along with the expansion of the application field of resin molded products and the trend toward higher added value, the demand for higher functionality of the cured resin layer (hard coat layer) is increasing. There is a demand for imparting antifouling properties. By imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, this makes it difficult to stain, or even if it stains, it can be easily removed.
ハードコート層に防汚性を付与する方法としては、一旦形成されたハードコート層表面に含フッ素防汚剤を塗工及び/又は定着させる方法が広く用いられているが、含フッ素硬化性成分を硬化前の硬化性樹脂組成物に添加し、これを塗布硬化させることでハードコート層の形成と防汚性の付与を同時に行う方法についても検討されてきた。例えば、特開平6-211945号公報(特許文献1)には、アクリル系の硬化性樹脂組成物にフルオロアルキルアクリレートを添加、硬化させることで防汚性を付与したハードコート層の製造が示されている。 As a method for imparting antifouling properties to the hard coat layer, a method of coating and/or fixing a fluorine-containing antifouling agent on the surface of the hard coat layer once formed is widely used. is added to a curable resin composition before curing, followed by coating and curing to simultaneously form a hard coat layer and impart antifouling properties. For example, Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1) discloses the production of a hard coat layer imparted with antifouling properties by adding fluoroalkyl acrylate to a curable acrylic resin composition and curing the composition. ing.
近年、こうした含フッ素アクリル化合物を配合した防汚性に優れる活性エネルギー線硬化性組成物は、用途が大きく拡大してきており、新たな機能が求められてきている。 In recent years, active energy ray-curable compositions containing such fluorine-containing acrylic compounds and having excellent antifouling properties have been widely used, and new functions have been required.
このように大きく用途範囲が広がることでハードコート、特に大型ディスプレイ表面の防汚処理、スマートフォンやタブレットなどの携帯用情報機器のディスプレイや筐体の表面処理においては、撥水性に代表される防汚性能、滑り性に代表される耐摩耗性についてより高い性能が求められてきている。これらの要求に対応する一つの手段はよりフッ素変性の高い成分を表面に配列させることである。しかし、単一構造の含フッ素アクリル化合物でフッ素含有率を増加させると、フッ素化されていないハードコート剤の他成分に対する溶解性が低下し、塗工表面に欠損等の不均一部分による塗工不良が発生する。
なお、本発明に関連する従来技術として、上述した文献と共に下記文献が挙げられる。Due to the widening of the range of applications, hard coatings, especially antifouling treatment on the surface of large displays, and surface treatment of displays and housings of portable information devices such as smartphones and tablets, are antifouling represented by water repellency. Higher performance is required for wear resistance represented by performance and slipperiness. One means of meeting these demands is to arrange more fluorine-modified components on the surface. However, when the fluorine content of a single structure fluorine-containing acrylic compound is increased, the solubility in other components of the non-fluorinated hard coating agent decreases, resulting in uneven coating such as defects on the coating surface. A defect occurs.
In addition to the documents mentioned above, the following documents can be cited as conventional techniques related to the present invention.
本発明は、上記事情に鑑みなされたもので、安定した溶解性を有し、硬化後に高い防汚性、及び高い滑り性を有する含フッ素硬化性組成物、並びに該組成物の硬化被膜を表面に有する物品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. The purpose is to provide goods that have
本発明者は、このような硬化性樹脂組成物に防汚性を付与できるフッ素化合物として、様々な開発を進めており、例えば、特開2010-53114号公報(特許文献2)、特開2010-138112号公報(特許文献3)、特開2010-285501号公報(特許文献4)に示す光硬化可能なフッ素化合物を提案している。これらの防汚特性、滑り性を向上させるには化合物中のフッ素成分の含有率を増加させる方法が考えられる。しかし、上述したように単一構造の含フッ素アクリル化合物で非フッ素化成分への溶解性を向上させた場合、塗工表面へのフッ素成分の濃縮が起きにくくなり、結果として防汚性能が発現しにくくなってしまう場合がある。 The present inventors have been developing various fluorine compounds that can impart antifouling properties to such curable resin compositions. JP-A-138112 (Patent Document 3) and JP-A-2010-285501 (Patent Document 4) have proposed photocurable fluorine compounds. In order to improve these antifouling properties and slipperiness, it is conceivable to increase the content of the fluorine component in the compound. However, as mentioned above, when the solubility in non-fluorinated components is improved with a single-structure fluorine-containing acrylic compound, the concentration of fluorine components on the coated surface becomes difficult, and as a result, the antifouling performance is exhibited. It may become difficult to do so.
そこで、本発明者は、更なる検討を重ねた結果、フルオロポリエーテルを主鎖に持つ直鎖ポリマーであって、末端に1個又は2個の(メタ)アクリル基を有し、1分子中に含まれる(メタ)アクリル基の個数の平均値が2個以下であり、フッ素含有率が48質量%以上62質量%未満の化合物からなる成分(A)、フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの末端に2個以上の(メタ)アクリル基を有し、1分子中に平均して4~10個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる成分(B)、及びフルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物からなる成分(C)をそれぞれ所定の配合比率で含有する含フッ素硬化性組成物が、防汚性・撥水性に優れ、低い動摩擦係数を有する硬化被膜を形成し得ることを見出し、本発明をなすに至った。 Therefore, as a result of further studies, the present inventors have found that a linear polymer having a fluoropolyether in the main chain, having one or two (meth)acrylic groups at the ends, The average number of (meth) acrylic groups contained in is 2 or less, and the component (A) made of a compound having a fluorine content of 48% by mass or more and less than 62% by mass, a straight chain having a fluoropolyether It has two or more (meth)acrylic groups at each end in one molecule of the chain polymer, has an average of 4 to 10 (meth)acrylic groups in one molecule, and has a fluorine content of 25. A component (B) composed of a compound with a mass % or more and less than 45 mass %, and a non-fluorinated acrylic compound that does not contain a fluoropolyether structure and has an average of 2 or more (meth) acrylic groups in one molecule. It was found that a fluorine-containing curable composition containing component (C) in a predetermined blending ratio can form a cured film having excellent antifouling properties and water repellency and a low coefficient of dynamic friction. Arrived.
従って、本発明は、下記の含フッ素硬化性組成物、及び該組成物の硬化被膜を表面に有する物品を提供する。
[1]
フルオロポリエーテルを主鎖に持つ直鎖ポリマーであって、分子鎖の片末端又は両末端に1個又は2個の(メタ)アクリル基を有し、1分子中に含まれる(メタ)アクリル基の個数の平均値が2個以下であり、フッ素含有率が48質量%以上62質量%未満の化合物からなる、下記一般式(1)又は(2)
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(式中、Rf1はフッ素原子、又は酸素原子を含んでいてもよい炭素数1~8の1価の含フッ素アルキル基であり、Rf2は下記の2種類の繰り返し単位
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000の2価のパーフルオロポリエーテル基である。Z1は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基、-C(=O)-及び-C(=O)O-から選ばれる連結基であり、該2価の炭化水素基は途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。X1は独立に酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を有する1価の有機基であり、X2は水酸基又はX1である。)
で表される成分(A)、
フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの分子鎖末端にそれぞれ2個以上の(メタ)アクリル基を有し、1分子中に平均して4~10個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる、下記一般式(3)
で表される成分(B)、及び
フルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物からなる成分(C)を必須成分とし、成分(C)100質量部に対して、成分(A)と成分(B)の配合量の合計が0.1~10質量部であり、かつ成分(B)100質量部に対する成分(A)の配合量が3~50質量部である含フッ素硬化性組成物。
[2]
更に、光重合開始剤(D)を含有する[1]に記載の含フッ素硬化性組成物。
[3]
成分(B)100質量部に対する成分(A)の配合量が5.26~25質量部である[1]又は[2]に記載の含フッ素硬化性組成物。
[4]
成分(A)において、一般式(1)又は(2)中のZ1が、下記のいずれかの構造である[1]~[3]のいずれかに記載の含フッ素硬化性組成物。
-C(=O)-
-C(=O)O-
-C(=O)OCH2-
-C(=O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2-
[5]
成分(A)において、一般式(1)又は(2)中のX1が、下記のいずれかで示されるものである[1]~[4]のいずれかに記載の含フッ素硬化性組成物。
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH 2
-CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
-C(CH3)[CH2OC(=O)CH=CH2] 2
-C(CH2CH3)[CH2OC(=O)CH=CH2]2
-C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2
[6]
成分(A)において、一般式(1)又は(2)で表される含フッ素アクリル化合物が、下記のいずれかで示されるものである[1]~[5]のいずれかに記載の含フッ素硬化性組成物。
Rf1ORf2CF2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2
CH2=C(CH3)C(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)CH=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)CH=CH2
CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
(式中、Rf1、Rf2は上記と同じである。)
[7]
成分(B)において、一般式(3)中のZ3が、下記式のいずれかで表されるものである[1]~[6]のいずれかに記載の含フッ素硬化性組成物。
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
[8]
成分(B)において、一般式(3)中のQ1が、下記式で表されるものである[1]~[7]のいずれかに記載の含フッ素硬化性組成物。
[9]
成分(B)において、一般式(3)で表される含フッ素アクリル化合物が、下記一般式(4)又は(5)で表される含フッ素アクリル化合物である[1]~[8]のいずれかに記載の含フッ素硬化性組成物。
[10]
成分(C)の非フッ素化アクリル化合物が、1分子中に2個以上の(メタ)アクリル基を有しウレタン結合を有さない多官能アクリル化合物、又はこの多官能アクリル化合物と脂肪族ポリイソシアネートと水酸基を有するアクリル化合物とを反応させて得られた1分子中に3個以上の(メタ)アクリル基を有する多官能ウレタンアクリレート類、又は前記多官能アクリル化合物とウレタンアクリレート類とを含む2種類以上のアクリル化合物の混合物である[1]~[9]のいずれかに記載の含フッ素硬化性組成物。
[11]
[1]~[10]のいずれかに記載の含フッ素硬化性組成物の硬化被膜を表面に有する物品。
Accordingly, the present invention provides the following fluorine-containing curable composition and an article having a cured film of the composition on its surface.
[1]
A linear polymer having a fluoropolyether as the main chain, having one or two (meth)acrylic groups at one or both ends of the molecular chain, and the (meth)acrylic group contained in one molecule The following general formula (1) or (2) consisting of a compound having an average number of 2 or less and a fluorine content of 48% by mass or more and less than 62% by mass
Rf 1 -O-Rf 2 -CF 2 -Z 1 -X 1 (1)
X 2 -Z 1 -CF 2 O-Rf 2 -CF 2 -Z 1 -X 1 (2)
(In the formula, Rf 1 is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms which may contain an oxygen atom, and Rf 2 is one of the following two types of repeating units —CF 2 O—
-CF2CF2O- _
is a randomly arranged divalent perfluoropolyether group with a molecular weight of 600 to 20,000. Z 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom, -C(=O)- and - A linking group selected from C(=O)O—, the divalent hydrocarbon group may contain a cyclic structure in the middle, and some of the hydrogen atoms bonded to the carbon atoms are substituted with fluorine atoms. may X 1 is independently a monovalent organic group having a (meth)acryl group optionally containing an oxygen atom and/or a nitrogen atom, and X 2 is a hydroxyl group or X 1 . )
Component (A) represented by
Each molecule of a linear polymer having a fluoropolyether as a main chain has two or more (meth)acrylic groups at each molecular chain end, and an average of 4 to 10 (meth)acrylic groups per molecule. ) The following general formula (3), which has an acrylic group and is composed of a compound having a fluorine content of 25% by mass or more and less than 45% by mass
A component (B) represented by and a component (C) consisting of a non-fluorinated acrylic compound that does not contain a fluoropolyether structure and has an average of two or more (meth)acrylic groups in one molecule (C) as an essential component and the total amount of component (A) and component (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of component (C), and component (A ) in an amount of 3 to 50 parts by mass.
[2]
The fluorine-containing curable composition according to [1], further comprising a photopolymerization initiator (D).
[3]
The fluorine-containing curable composition according to [1] or [2], wherein the amount of component (A) is 5.26 to 25 parts by mass per 100 parts by mass of component (B).
[4]
The fluorine-containing curable composition according to any one of [1] to [3], wherein in component (A), Z 1 in general formula (1) or (2) has any of the following structures.
-C(=O)-
-C(=O)O-
-C(=O) OCH2-
-C ( =O) OCH2CH2-
-CH2-
-CH 2 O-
-CH2OCH2- _
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OC (=O)NH-
-CH2OC ( =O) NHCH2CH2-
[5]
The fluorine-containing curable composition according to any one of [1] to [4], wherein in component (A), X 1 in general formula (1) or (2) is any of the following: .
-OC(=O)CH= CH2
-OC(=O)C( CH3 )= CH2
- CH[ CH2OC (=O)CH= CH2 ][ CH2OC (=O)C( CH3 )= CH2 ]
-C( CH3 )[ CH2OC (=O)CH= CH2 ] 2
- C( CH2CH3 )[ CH2OC (=O)CH = CH2 ] 2
-C( CH2CH3 )[ CH2OC ( = O)C( CH3 )= CH2 ] 2
[6]
The fluorine-containing acryl compound represented by formula (1) or (2) in component (A) is any one of the following: Curable composition.
Rf1ORf2CF2CH2OC (= O ) CH = CH2
Rf1ORf2CF2CH2OC (= O ) C ( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O )CH = CH2
HOCH2CF2ORf2CF2CH2OC ( = O )C ( CH3 ) = CH2
Rf1ORf2CF2C ( = O) OCH2CH2OC (= O )CH = CH2
Rf1ORf2CF2C ( =O) OCH2CH2OC ( = O )C( CH3 )= CH2
HOCH2CF2ORf2CF2C ( = O) OCH2CH2OC ( = O )CH = CH2
HOCH2CF2ORf2CF2C ( = O) OCH2CH2OC ( = O )C( CH3 ) = CH2
Rf1ORf2CF2C (=O)OCH[ CH2OC (=O)CH= CH2 ][ CH2OC (= O ) C ( CH3 )= CH2 ]
Rf1ORf2CF2CH2OC ( = O) NHCH2CH2OC ( = O )CH = CH2
Rf1ORf2CF2CH2OC ( = O) NHCH2CH2OC ( = O )C( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O) NHCH2CH2OC (= O ) CH = CH2
HOCH2CF2ORf2CF2CH2OC (=O) NHCH2CH2OC ( = O ) C ( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O)NHC ( CH3 )[ CH2OC ( = O )CH= CH2 ] 2
CH2 =C( CH3 ) C ( =O)OCH2CF2ORf2CF2CH2OC(= O )C( CH3 ) = CH2
CH2 = CHC (= O ) OCH2CF2ORf2CF2CH2OC (=O)C( CH3 ) = CH2
CH2 = CHC ( =O) OCH2CF2ORf2CF2CH2OC (=O)CH = CH2
CH2 = CHC ( = O ) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OCH2OC( = O) CH = CH2
CH2 =C ( CH3 ) C ( = O ) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OCH2OC(= O )C( CH3 ) = CH2
CH2 = CHC (=O) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OC( = O ) NHCH2CH2OC ( = O ) CH = CH2
(In the formula, Rf 1 and Rf 2 are the same as above.)
[7]
The fluorine-containing curable composition according to any one of [1] to [6], wherein in component (B), Z 3 in general formula (3) is represented by any one of the following formulae.
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _
[8]
The fluorine-containing curable composition according to any one of [1] to [7], wherein in component (B), Q 1 in general formula (3) is represented by the following formula.
[9]
Any of [1] to [8], wherein the fluorine-containing acrylic compound represented by the general formula (3) in the component (B) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5) The fluorine-containing curable composition according to 1.
[10]
The non-fluorinated acrylic compound of component (C) is a polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and no urethane bond, or this polyfunctional acrylic compound and an aliphatic polyisocyanate. Polyfunctional urethane acrylates having 3 or more (meth)acrylic groups in one molecule obtained by reacting with an acrylic compound having a hydroxyl group, or two types including the polyfunctional acrylic compound and urethane acrylates The fluorine-containing curable composition according to any one of [1] to [9], which is a mixture of the above acrylic compounds.
[11]
An article having on its surface a cured film of the fluorine-containing curable composition according to any one of [1] to [10].
本発明の含フッ素硬化性組成物は、安定した溶解性を有し、高い防汚性、汚れ拭き取り性、滑り性を持った硬化被膜を与えることができる。 The fluorine-containing curable composition of the present invention has stable solubility and can provide a cured film having high antifouling properties, stain-wiping properties and slipperiness.
本発明の含フッ素硬化性組成物は、フルオロポリエーテルを主鎖に持つ直鎖ポリマーであって、分子鎖の片末端又は両末端に1個又は2個の(メタ)アクリル基を有し、1分子中に含まれる(メタ)アクリル基の個数の平均値が2個以下であり、フッ素含有率が48質量%以上62質量%未満の化合物からなる成分(A)、フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの分子鎖末端(即ち、分子鎖両末端)にそれぞれ2個以上の(メタ)アクリル基を有し、1分子中に平均して4~10個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる成分(B)、及びフルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物からなる成分(C)から構成され、上記成分(A)、(B)、(C)を必須成分とする。 The fluorine-containing curable composition of the present invention is a linear polymer having a fluoropolyether as a main chain, and has one or two (meth)acrylic groups at one or both ends of the molecular chain, The average number of (meth)acrylic groups contained in one molecule is 2 or less, and the component (A) made of a compound having a fluorine content of 48% by mass or more and less than 62% by mass, and a fluoropolyether as a main chain It has two or more (meth)acrylic groups at each molecular chain end (that is, both molecular chain ends) in one molecule of the linear polymer having an average of 4 to 10 in one molecule A component (B) comprising a compound having a (meth) acrylic group and having a fluorine content of 25% by mass or more and less than 45% by mass, and a component (B) containing no fluoropolyether structure and having an average of 2 or more in one molecule It is composed of a component (C) comprising a non-fluorinated acrylic compound having a (meth)acrylic group, and the components (A), (B) and (C) are essential components.
本発明において、「アクリル化合物」とは、アクリル基、メタクリル基を有する化合物の総称であり、また、「(メタ)アクリル基」とは、アクリル基とメタクリル基の一方又は両方を示し、「(メタ)アクリル酸」とは、アクリル酸とメタクリル酸の一方又は両方を示し、「(メタ)アクリレート」とは、アクリレートとメタクリレートの一方又は両方を示す。更に、「アクリレート類」とは、アクリレート、メタクリレートを有する化合物の総称である。 In the present invention, "acrylic compound" is a general term for compounds having an acrylic group and a methacrylic group, and "(meth)acrylic group" indicates one or both of an acrylic group and a methacrylic group, and "( “Meth)acrylic acid” refers to one or both of acrylic acid and methacrylic acid, and “(meth)acrylate” refers to one or both of acrylate and methacrylate. Furthermore, "acrylates" is a general term for compounds having acrylates and methacrylates.
なお、本発明において、成分(A)、(B)、(C)の各成分はそれぞれ単一の化合物である必要はなく、例えば配合における質量を考える場合は成分(A)、(B)、(C)のそれぞれの条件に一致する複数の化合物の混合物の配合量の合計をそれぞれ各成分量として考えればよい。 In the present invention, each component of components (A), (B), and (C) does not need to be a single compound. The total amount of a mixture of a plurality of compounds that meet the respective conditions of (C) may be considered as the amount of each component.
〔成分(A)〕
本発明の含フッ素硬化性組成物における第一の必須成分である成分(A)は、フルオロポリエーテルを主鎖に持つ直鎖ポリマーであって、分子鎖の片末端又は両末端に1個又は2個の(メタ)アクリル基を有し、1分子中に含まれる(メタ)アクリル基の個数の平均値が2個以下(1~2個)であり(即ち、該直鎖ポリマーの分子鎖両末端にそれぞれ1個ずつの(メタ)アクリル基を有するか、あるいは、分子鎖の片末端に1個又は2個の(メタ)アクリル基を有する)、フッ素含有率が48質量%以上62質量%未満の化合物からなる。[Component (A)]
Component (A), which is the first essential component in the fluorine-containing curable composition of the present invention, is a linear polymer having a fluoropolyether as a main chain, and has one or both ends of the molecular chain. It has two (meth)acrylic groups, and the average number of (meth)acrylic groups contained in one molecule is 2 or less (1 to 2) (that is, the molecular chain of the linear polymer one (meth)acrylic group at each end of the molecular chain, or one or two (meth)acrylic groups at one end of the molecular chain), with a fluorine content of 48% by mass or more and 62% by mass % of compounds.
ここで、成分(A)の化合物のフッ素含有率は、48質量%以上62質量%未満であり、好ましくは55質量%以上61.5質量%以下であり、より好ましくは57質量%以上61質量%以下である。フッ素含有率が48質量%未満であると成分(A)を使用しない場合と比較して防汚性能の向上が不十分であり、62質量%以上であると成分(C)に対する溶解性が不足し、硬化被膜が平滑な塗工面を得ることが困難である。なお、本発明において、フッ素含有率は、19F-NMR及び1H-NMRから求められる化合物の分子式から算出した数平均分子量に対する分子中のフッ素原子の質量%値である(以下、同じ)。Here, the fluorine content of the compound of component (A) is 48% by mass or more and less than 62% by mass, preferably 55% by mass or more and 61.5% by mass or less, more preferably 57% by mass or more and 61% by mass. % or less. If the fluorine content is less than 48% by mass, the antifouling performance is insufficient compared to the case where the component (A) is not used, and if it is 62% by mass or more, the solubility in the component (C) is insufficient. However, it is difficult to obtain a smooth coated surface of the cured film. In the present invention, the fluorine content is the mass % value of fluorine atoms in the molecule with respect to the number average molecular weight calculated from the molecular formula of the compound obtained from 19 F-NMR and 1 H-NMR (hereinafter the same).
このような化合物としては、例えば下記一般式(1)又は(2)で表される含フッ素アクリル化合物を示すことができる。
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)Examples of such compounds include fluorine-containing acrylic compounds represented by the following general formula (1) or (2).
Rf 1 -O-Rf 2 -CF 2 -Z 1 -X 1 (1)
X 2 -Z 1 -CF 2 O-Rf 2 -CF 2 -Z 1 -X 1 (2)
上記式(1)中、Rf1はフッ素原子、又は酸素原子を含んでいてもよい炭素数1~8、好ましくは炭素数1~6の1価の含フッ素アルキル基であり、具体的には、フッ素原子の他に、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロイソプロピル基、パーフルオロブチル基、パーフルオロペンチル基、パーフルオロヘキシル基、及び
CF3OCF2CF2-
CF3OCF2CF2CF2-
CF3CF2OCF2CF2-
(CF3)2CFOCF2CF2-
CF3OCF2CF2CF2CF2-
CF3CF2OCF2CF2CF2-
CF3CF2CF2OCF2CF2-
(CF3)2CFCF2OCF2CF2-
CF3CF2CF2CF2OCF2CF2-
CF3CF2CF2OCF2CF2CF2-
が挙げられ、これらの中でも特にCF3-、CF3CF2-が好ましい。In the above formula (1), Rf 1 is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which may contain an oxygen atom. , a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, and a CF 3 OCF 2 CF 2 −
CF3OCF2CF2CF2- _ _ _
CF3CF2OCF2CF2- _ _ _
( CF3 ) 2CFOCF2CF2-
CF3OCF2CF2CF2CF2- _ _ _ _
CF3CF2OCF2CF2CF2- _ _ _ _
CF3CF2CF2OCF2CF2- _ _ _ _
( CF3 ) 2CFCF2OCF2CF2- _
CF3CF2CF2CF2OCF2CF2 - _ _ _ _
CF3CF2CF2OCF2CF2CF2 - _ _ _ _
Among these, CF 3 — and CF 3 CF 2 — are particularly preferred.
上記式(1)、(2)中、Rf2は以下の2種類の繰り返し単位
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000、好ましくは1,200~10,000の2価のパーフルオロポリエーテル基であり、例えば以下のように表すことができる。
-(CF2O)m(CF2CF2O)n-In the above formulas (1) and (2), Rf 2 is the following two types of repeating units -CF 2 O-
-CF2CF2O- _
is a randomly arranged divalent perfluoropolyether group having a molecular weight of 600 to 20,000, preferably 1,200 to 10,000, and can be represented, for example, as follows.
-( CF2O ) m ( CF2CF2O ) n-
mは1~200の整数、好ましくは6~50の整数であり、nは1~170の整数、好ましくは6~50の整数であり、m+nは6~201の整数、好ましくは12~100の整数である、m、n及びm+nの値はこれより小さすぎると硬化組成物に防汚性を付与する効果が小さくなり、これよりも多すぎると非フッ素化成分との相溶性が悪くなり、塗工液の濁りや塗工不良の原因となる。これらm及びnの値は分布を持っていてもよく、分布を持つ場合は19F-NMR等から求められるm+nの値が数平均で上記範囲を満たすことが好ましい。m is an integer of 1 to 200, preferably an integer of 6 to 50, n is an integer of 1 to 170, preferably an integer of 6 to 50, m+n is an integer of 6 to 201, preferably an integer of 12 to 100 If the values of m, n, and m+n, which are integers, are too small, the effect of imparting antifouling properties to the cured composition will be small, and if they are too large, compatibility with non-fluorinated components will be poor, It causes turbidity of the coating liquid and poor coating. The values of m and n may have a distribution, and if they have a distribution, it is preferable that the value of m+n determined by 19 F-NMR or the like satisfies the above range as a number average.
上記式(1)、(2)中、Z1は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基、-C(=O)-及び-C(=O)O-から選ばれる連結基であり、該2価の炭化水素基は途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。このようなZ1として、好適な構造としては、以下に示す構造群が挙げられる。In the above formulas (1) and (2), Z 1 is a divalent hydrocarbon having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom. A linking group selected from -C(=O)- and -C(=O)O-, wherein the divalent hydrocarbon group may contain a cyclic structure in the middle, hydrogen bonded to a carbon atom A part of the atoms may be substituted with fluorine atoms. Examples of suitable structures for such Z 1 include the following structural groups.
-C(=O)-
-C(=O)O-
-C(=O)OCH2-
-C(=O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2--C(=O)-
-C(=O)O-
-C(=O) OCH2-
-C ( =O) OCH2CH2-
-CH2-
-CH 2 O-
-CH2OCH2- _
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OC (=O)NH-
-CH2OC ( =O) NHCH2CH2-
これらの中でも特に
-CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2-
が好ましい。Among these, -CH 2 -
-CH2OC (=O)NH-
-CH2OC ( =O) NHCH2CH2-
is preferred.
上記式(1)、(2)中、X1は独立に酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を好ましくは1個又は2個有する1価の有機基であり、但し、1分子中に1個又は2個の前記1価の有機基を有する。また、上記式(2)中、X2は水酸基又はX1である。In the above formulas (1) and (2), X 1 is a monovalent organic group having preferably one or two (meth)acrylic groups which may independently contain an oxygen atom and/or a nitrogen atom. However, it has 1 or 2 said monovalent organic groups in 1 molecule. Moreover, in said formula (2), X2 is a hydroxyl group or X1 .
X1の好ましい構造として、具体的には、下記の構造が例示される。
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH 2
-CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
-C(CH3)[CH2OC(=O)CH=CH2] 2
-C(CH2CH3)[CH2OC(=O)CH=CH2]2
-C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2
Preferred structures of X 1 are specifically exemplified by the following structures.
-OC(=O)CH= CH2
-OC(=O)C( CH3 )= CH2
- CH[ CH2OC (=O)CH= CH2 ][ CH2OC (=O)C( CH3 )= CH2 ]
-C( CH3 )[ CH2OC (=O)CH= CH2 ] 2
- C( CH2CH3 )[ CH2OC (=O)CH = CH2 ] 2
-C( CH2CH3 )[ CH2OC ( = O)C( CH3 )= CH2 ] 2
特に好ましくは
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH2
である。-OC(=O)CH=CH 2 is particularly preferred
-OC(=O)C( CH3 )= CH2
is.
X2の好ましい構造として、具体的には、下記の構造が例示される。
HO-
CH2=C(CH3)C(=O)O-
CH2=CHC(=O)O-Preferred structures of X 2 are specifically exemplified by the following structures.
HO-
CH2 =C( CH3 )C(=O)O-
CH2 =CHC(=O)O-
このような成分(A)として、更に具体的には、以下の構造群で示される化合物を挙げることができる。
Rf1ORf2CF2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2
CH2=C(CH3)C(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)CH=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)CH=CH2
CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
(式中、Rf1、Rf2は前記の通りであるが、成分(A)に該当する化合物としてのフッ素含有率の平均値が55質量%以上62質量%未満のものが特に好ましい。)More specific examples of such component (A) include compounds represented by the following structural groups.
Rf1ORf2CF2CH2OC (= O ) CH = CH2
Rf1ORf2CF2CH2OC (= O ) C ( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O )CH = CH2
HOCH2CF2ORf2CF2CH2OC ( = O )C ( CH3 ) = CH2
Rf1ORf2CF2C (=O) OCH2CH2OC (= O ) CH = CH2
Rf1ORf2CF2C ( = O) OCH2CH2OC (= O )C( CH3 )= CH2
HOCH2CF2ORf2CF2C ( = O) OCH2CH2OC ( = O )CH = CH2
HOCH2CF2ORf2CF2C ( = O) OCH2CH2OC ( = O )C( CH3 ) = CH2
Rf1ORf2CF2C (=O)OCH[ CH2OC (=O)CH= CH2 ][ CH2OC (= O ) C ( CH3 )= CH2 ]
Rf1ORf2CF2CH2OC ( = O) NHCH2CH2OC ( = O )CH = CH2
Rf1ORf2CF2CH2OC ( =O) NHCH2CH2OC ( = O )C( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O) NHCH2CH2OC (= O ) CH = CH2
HOCH2CF2ORf2CF2CH2OC (=O) NHCH2CH2OC ( = O ) C ( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O)NHC ( CH3 )[ CH2OC ( = O )CH= CH2 ] 2
CH2 =C( CH3 ) C ( =O)OCH2CF2ORf2CF2CH2OC(= O )C( CH3 ) = CH2
CH2 = CHC (= O ) OCH2CF2ORf2CF2CH2OC (=O)C( CH3 ) = CH2
CH2 = CHC ( =O) OCH2CF2ORf2CF2CH2OC (=O)CH = CH2
CH2 = CHC ( = O ) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OCH2OC( = O ) CH = CH2
CH2 =C ( CH3 ) C ( = O ) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OCH2OC(= O )C( CH3 ) = CH2
CH2 = CHC (=O) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OC( = O ) NHCH2CH2OC ( = O ) CH = CH2
(In the formula, Rf 1 and Rf 2 are as described above, but compounds having an average fluorine content of 55% by mass or more and less than 62% by mass are particularly preferred as compounds corresponding to component (A).)
上記成分(A)である下記一般式(1)又は(2)
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(式中、Rf1、Rf2、Z1、X1、X2は上記と同じである。)
で表される含フッ素アクリル化合物の好適な合成方法としては、例えば、下記一般式(6)又は(7)
Rf1-O-Rf2-CF2-CH2-OH (6)
HO-CH2-CF2O-Rf2-CF2-CH2-OH (7)
(式中、Rf1、Rf2は上記と同じである。)
で表される含フッ素アルコール化合物に、一つは下記一般式(8)
CH2=CR3C(=O)X (8)
(式中、R3は上記と同じであり、Xはフッ素原子、塩素原子、臭素原子等のハロゲン原子である。)
で表される(メタ)アクリル酸ハライドを反応させて、エステルを形成する方法、もう一つは下記一般式(9)
CH2=CR3C(=O)OCH2CH2-N=C=O (9)
(式中、R3は上記と同じである。)
で表される(メタ)アクリル基を含有するイソシアネート化合物を反応させる方法が挙げられ、これらの方法により、上記式(1)又は(2)で表される含フッ素アクリル化合物を得ることができる。The following general formula (1) or (2), which is the component (A)
Rf 1 -O-Rf 2 -CF 2 -Z 1 -X 1 (1)
X 2 -Z 1 -CF 2 O-Rf 2 -CF 2 -Z 1 -X 1 (2)
(In the formula, Rf 1 , Rf 2 , Z 1 , X 1 and X 2 are the same as above.)
As a suitable method for synthesizing the fluorine-containing acrylic compound represented by, for example, the following general formula (6) or (7)
Rf1 -O-Rf2- CF2 - CH2 -OH (6)
HO--CH 2 --CF 2 O--Rf 2 --CF 2 --CH 2 --OH (7)
(In the formula, Rf 1 and Rf 2 are the same as above.)
One of the fluorine-containing alcohol compounds represented by the following general formula (8)
CH2 = CR3C (=O)X (8)
(In the formula, R3 is the same as above, and X is a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.)
A method of forming an ester by reacting a (meth)acrylic acid halide represented by the following general formula (9)
CH2 = CR3C (=O) OCH2CH2 - N=C=O (9)
(In the formula, R 3 is the same as above.)
A method of reacting an isocyanate compound containing a (meth)acrylic group represented by can be used to obtain a fluorine-containing acrylic compound represented by the above formula (1) or (2).
ここで、式(8)で表される(メタ)アクリル酸ハライドとしては、下記に示すものが挙げられる。
CH2=CHC(=O)X
CH2=C(CH3)C(=O)X
(式中、Xは上記と同じである。)
特にアクリル酸クロリド、メタクリル酸クロリドが好ましい。Here, examples of the (meth)acrylic acid halide represented by formula (8) include those shown below.
CH2 =CHC(=O)X
CH2 =C( CH3 )C(=O)X
(In the formula, X is the same as above.)
Acrylic acid chloride and methacrylic acid chloride are particularly preferred.
また、式(9)で表される(メタ)アクリル基を含有するイソシアネート化合物としては、下記に示すものが挙げられる。
CH2=CHC(=O)OCH2CH2-N=C=O
CH2=C(CH3)C(=O)OCH2CH2-N=C=OExamples of the (meth)acrylic group-containing isocyanate compound represented by formula (9) include those shown below.
CH2 =CHC(=O) OCH2CH2 - N=C=O
CH2 =C( CH3 )C(=O) OCH2CH2 - N=C=O
これらの(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物は、含フッ素アルコール化合物の水酸基量の合計に対して等モル以上を仕込み反応させ、水酸基をすべて反応させてもよいが、式(7)の化合物においては含フッ素アルコール化合物1モルに対して平均して1モル以上の(メタ)アクリル基を導入させればよく、水酸基を過剰とさせることで、未反応の(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物を残存させないようにしてもよい。具体的には、反応系中の含フッ素アルコール化合物量をxモル、含フッ素アルコール化合物の水酸基量の合計をyモルとした場合、(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物はxモル以上2yモル以下であることが望ましく、特に好ましくは0.6yモル以上1.4yモル以下である。少なすぎる場合、(メタ)アクリル基が全く導入されない含フッ素アルコール化合物が残存する可能性が高くなり、生成物の溶解性が低くなってしまう可能性がある。多すぎる場合、未反応の(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物の残存の除去が困難となる。 These (meth)acrylic acid halides or (meth)acrylic group-containing isocyanate compounds may be reacted in an equimolar amount or more with respect to the total amount of hydroxyl groups in the fluorine-containing alcohol compound, and all the hydroxyl groups may be reacted. In the compound of the formula (7), it suffices to introduce an average of 1 mol or more (meth)acrylic groups per 1 mol of the fluorine-containing alcohol compound. ) The isocyanate compound containing acrylic acid halide or (meth)acrylic group may not remain. Specifically, when the amount of fluorine-containing alcohol compound in the reaction system is x mol, and the total amount of hydroxyl groups of the fluorine-containing alcohol compound is y mol, (meth)acrylic acid halide or isocyanate containing (meth)acrylic group The amount of the compound is preferably x mol or more and 2 y mol or less, and particularly preferably 0.6 y mol or more and 1.4 y mol or less. If the amount is too small, there is a high possibility that the fluorine-containing alcohol compound in which no (meth)acrylic group is introduced remains, and the solubility of the product may become low. If the amount is too large, it becomes difficult to remove unreacted (meth)acrylic acid halides or residual isocyanate compounds containing (meth)acrylic groups.
これらの反応は、必要に応じて適当な溶剤で希釈して反応を行ってもよい。このような溶剤としては、含フッ素アルコール化合物の水酸基、(メタ)アクリル酸ハライドのハロゲン原子、(メタ)アクリル基を含有するイソシアネート化合物のイソシアネート基と反応しない溶剤であれば特に制限なく用いることができ、具体的には、トルエン、キシレン、イソオクタンなどの炭化水素系溶剤、テトラヒドロフラン(THF)、ジイソプロピルエーテル、ジブチルエーテル等のエーテル系溶剤、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、m-キシレンヘキサフロライド(別名:ヘキサフルオロメタキシレン)、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などが挙げられる。この溶剤は、反応後に減圧留去等の公知の手法で除去してもよく、目的の用途に応じてそのまま希釈溶液として使用してもよい。
溶剤の使用量は特に限定されないが、反応成分の全合計質量に対して10倍以下が好ましい。溶剤の使用量が多すぎると、反応速度が大幅に低下する危険がある。These reactions may be carried out by diluting with a suitable solvent as necessary. As such a solvent, any solvent that does not react with the hydroxyl group of the fluorine-containing alcohol compound, the halogen atom of the (meth)acrylic acid halide, or the isocyanate group of the isocyanate compound containing the (meth)acrylic group can be used without particular limitation. Specifically, hydrocarbon solvents such as toluene, xylene and isooctane; ether solvents such as tetrahydrofuran (THF), diisopropyl ether and dibutyl ether; Fluorine-modified aromatic hydrocarbon solvents such as ketone solvents, m-xylene hexafluoride (also known as hexafluorometa-xylene) and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. This solvent may be removed by a known technique such as distillation under reduced pressure after the reaction, or may be used as it is as a diluted solution depending on the intended use.
The amount of the solvent to be used is not particularly limited, but is preferably 10 times or less with respect to the total mass of the reaction components. If too much solvent is used, there is a danger that the reaction rate will be greatly reduced.
また、反応の際には、必要に応じて重合禁止剤を添加してもよい。重合禁止剤としては特に制限はないが、通常、アクリル化合物の重合禁止剤として用いられるものを用いることができる。具体的には、ヒドロキノン、ヒドロキノンモノメチルエーテル、4-tert-ブチルカテコール、ジブチルヒドロキシトルエン等を挙げることができる。
重合禁止剤の使用量は反応条件、反応後の精製条件、最終的な使用条件から決定すればよく、特に制限はされないが、通常、反応成分の全合計質量に対して0.01~5,000ppm、特に好ましくは0.1~500ppmである。Moreover, you may add a polymerization inhibitor as needed in the case of reaction. The polymerization inhibitor is not particularly limited, but those commonly used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.
The amount of the polymerization inhibitor to be used may be determined based on the reaction conditions, post-reaction purification conditions, and final use conditions, and is not particularly limited, but is usually 0.01 to 5,000,000,000,000,000,000,000,000, or 000 ppm, particularly preferably 0.1 to 500 ppm.
含フッ素アルコール化合物に(メタ)アクリル酸ハライドを反応させる場合、特にアクリル酸クロリド、メタクリル酸クロリドを反応させて、エステルを生成することが好ましい。該エステル生成反応は、上記反応中間体(含フッ素アルコール化合物)、受酸剤を混合攪拌しながら(メタ)アクリル酸ハライドを滴下して行う。受酸剤はトリエチルアミン、ピリジン、尿素などが使用できる。受酸剤の使用量は、(メタ)アクリル酸ハライドの仕込みモル数に対して0.9~3倍程度が望ましい。少なすぎるとトラップされない酸が多く残存することになり、多すぎると余剰となる受酸剤の除去が困難になる。 When a (meth)acrylic acid halide is reacted with a fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride or methacrylic acid chloride to produce an ester. The ester formation reaction is carried out by dropping the (meth)acrylic acid halide while mixing and stirring the reaction intermediate (fluorine-containing alcohol compound) and the acid acceptor. Usable acid acceptors include triethylamine, pyridine, and urea. The amount of the acid acceptor used is desirably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. If it is too small, a large amount of untrapped acid will remain, and if it is too large, it will be difficult to remove the surplus acid acceptor.
(メタ)アクリル酸ハライドの滴下は、反応混合物の温度を0~35℃に維持し、20~60分かけて行う。その後、更に30分~10時間攪拌を継続する。反応終了後、未反応の(メタ)アクリル酸ハライド、反応により発生した塩及び反応溶剤等を留去、吸着、ろ過、洗浄等の方法で除去することで、上記式(1)又は(2)で表される含フッ素アクリル化合物を得ることができる。 The dropwise addition of the (meth)acrylic acid halide is carried out over 20-60 minutes while maintaining the temperature of the reaction mixture at 0-35°C. Stirring is then continued for an additional 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, etc. are removed by a method such as distillation, adsorption, filtration, washing, etc. to obtain the above formula (1) or (2). A fluorine-containing acrylic compound represented by can be obtained.
また、反応停止の際に、メタノール、エタノール等のアルコール化合物を系内に添加し、未反応の(メタ)アクリル酸ハライドをエステル化してもよい。生成したアクリル酸エステル類は、未反応の(メタ)アクリル酸ハライド除去と同様の方法で除去できるが、残存させたまま使用することもできる。 Moreover, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The produced acrylic acid esters can be removed by the same method as for removing unreacted (meth)acrylic acid halides, but they can also be used as they remain.
含フッ素アルコール化合物と(メタ)アクリル基を含有するイソシアネート化合物との反応の場合には、含フッ素アルコール化合物と(メタ)アクリル基を含有するイソシアネート化合物を必要に応じて溶剤とともに攪拌し、反応を進行させる。 In the case of the reaction between the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group, the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group are stirred together with a solvent if necessary to initiate the reaction. proceed.
この反応において、反応の速度を増加するために適切な触媒を加えてもよい。触媒としては、例えば、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジオクトエート、ジオクチル錫ジアセテート、ジオクチル錫ジラウレート、ジオクチル錫ジオクテート、ジオクタン酸第1錫などのアルキル錫エステル化合物、テトライソプロポキシチタン、テトラn-ブトキシチタン、テトラキス(2-エチルヘキソキシ)チタン、ジプロポキシビス(アセチルアセトナ)チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステル又はチタンキレート化合物、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムモノブトキシアセチルアセトネートビス(エチルアセトアセテート)、ジルコニウムジブトキシビス(エチルアセトアセテート)、ジルコニウムテトラアセチルアセトネート、ジルコニウムキレート化合物等が例示される。これらはその1種に限定されず、2種もしくはそれ以上の混合物として使用できる。これらの触媒を反応物総質量に対して、0.01~2質量%、好ましくは0.05~1質量%加えることにより、反応速度を増加させることができる。 In this reaction, a suitable catalyst may be added to increase the rate of reaction. Examples of catalysts include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctoate, tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetona)titanium, titanium isopropoxyoctylene glycol, and other titanate esters or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxymonoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, zirconium chelate compounds and the like are exemplified. These are not limited to one type, and can be used as a mixture of two or more types. The reaction rate can be increased by adding 0.01 to 2% by weight, preferably 0.05 to 1% by weight, of these catalysts relative to the total weight of the reactants.
上記反応は0~120℃、好ましくは10~70℃の温度で、1分~500時間、好ましくは10分~48時間行う。反応温度が低すぎると反応速度が遅くなりすぎる場合があり、反応温度が高すぎると副反応として(メタ)アクリル基の重合が起きてしまう可能性がある。 The above reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may become too slow, and if the reaction temperature is too high, polymerization of (meth)acrylic groups may occur as a side reaction.
反応終了後、未反応のイソシアネート化合物及び反応溶剤等を留去、吸着、ろ過、洗浄等の方法で除去することで、上記式(1)又は(2)で表される含フッ素アクリル化合物を得ることができる。 After completion of the reaction, the unreacted isocyanate compound and reaction solvent are removed by distillation, adsorption, filtration, washing, or the like to obtain the fluorine-containing acrylic compound represented by the above formula (1) or (2). be able to.
また反応停止の際に、メタノール、エタノール等のアルコール化合物を系内に添加し、未反応のイソシアネート化合物とウレタン結合を形成させてもよい。生成したウレタンアクリレート類は、未反応のイソシアネート化合物と同様の方法で除去できるが、残存させたまま使用することもできる。 Also, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The produced urethane acrylates can be removed in the same manner as the unreacted isocyanate compound, but they can also be used as they remain.
〔成分(B)〕
本発明の含フッ素硬化性組成物における第二の必須成分である成分(B)は、フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの分子鎖末端(即ち、分子鎖両末端)にそれぞれ2個以上、好ましくは2~4個の(メタ)アクリル基を有し、1分子中に平均して4~10個、好ましくは4~8個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる。[Component (B)]
Component (B), which is the second essential component in the fluorine-containing curable composition of the present invention, is each molecular chain end in one molecule of a linear polymer having a fluoropolyether as a main chain (that is, both molecular chain ends). terminal) each have 2 or more, preferably 2 to 4 (meth)acrylic groups, and an average of 4 to 10, preferably 4 to 8 (meth)acrylic groups per molecule and a compound having a fluorine content of 25% by mass or more and less than 45% by mass.
ここで、成分(B)の化合物のフッ素含有率は、25質量%以上45質量%未満であり、好ましくは28質量%以上43質量%以下であり、より好ましくは33質量%以上42質量%以下である。フッ素含有率が25質量%未満であると成分(A)に対する溶解性が低下し、45質量%以上であると成分(C)に対する溶解性が低下するため、組成物全体として平滑に塗工することが困難となる。 Here, the fluorine content of the compound of component (B) is 25% by mass or more and less than 45% by mass, preferably 28% by mass or more and 43% by mass or less, more preferably 33% by mass or more and 42% by mass or less. is. If the fluorine content is less than 25% by mass, the solubility in component (A) is reduced, and if it is 45% by mass or more, the solubility in component (C) is reduced, so that the composition as a whole can be coated smoothly. becomes difficult.
このような化合物として、具体的には下記一般式(3)で表される含フッ素アクリル化合物を示すことができる。
上記式(3)中、Rf2は上記式(1)、(2)のRf2と同様である。In formula (3) above, Rf 2 is the same as Rf 2 in formulas (1) and (2) above.
上記式(3)中、R1は独立に水素原子又は炭素数1~8、好ましくは1~6の1価の炭化水素基であり、1価の炭化水素基として、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、フェニル基、トリル基、キシリル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基などが挙げられる。R1としては、水素原子及びメチル基が好ましい。In the above formula (3), R 1 is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and the monovalent hydrocarbon group is specifically methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, alkyl group such as octyl group, cycloalkyl group such as cyclohexyl group, vinyl group, allyl alkenyl groups such as propenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group and phenylethyl group. R 1 is preferably a hydrogen atom or a methyl group.
上記式(3)中、R2は独立に水素原子、又は酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を有する1価の有機基である。1価の有機基としては、末端に少なくとも1個、好ましくは1個又は2個の(メタ)アクリル基を有する基が好ましい。また、構造途中にアミド結合、エーテル結合、エステル結合などを有していてもよい。In the above formula (3), R 2 is independently a hydrogen atom or a monovalent organic group having a (meth)acrylic group which may contain an oxygen atom and/or a nitrogen atom. The monovalent organic group is preferably a group having at least one, preferably one or two (meth)acrylic groups at its terminals. Moreover, it may have an amide bond, an ether bond, an ester bond, or the like in the middle of the structure.
このような構造として、例えば、以下のものを挙げることができる。
CH2=CHC(=O)-
CH2=C(CH3)C(=O)-
CH2=CHC(=O)OCH2CH2-NHC(=O)-
CH2=C(CH3)C(=O)OCH2CH2-NHC(=O)-
CH2=C(CH3)C(=O)OCH2CH2OCH2CH2-NHC(=O)-
(CH2=CHC(=O)OCH2CH2)2C(CH3)-NHC(=O)-Examples of such structures include the following.
CH2 =CHC(=O)-
CH2 =C( CH3 )C(=O)-
CH2 =CHC(=O) OCH2CH2 - NHC(=O)-
CH2 =C( CH3 )C(=O) OCH2CH2 - NHC(=O)-
CH2 =C ( CH3 )C(=O) OCH2CH2OCH2CH2 - NHC (=O)-
( CH2 =CHC(= O)OCH2CH2)2C ( CH3 ) -NHC(=O)-
これらの中でも特に好適なのは、以下のものである。
CH2=CHC(=O)OCH2CH2-NHC(=O)-
CH2=C(CH3)C(=O)OCH2CH2-NHC(=O)-Among these, the following are particularly preferred.
CH2 =CHC(=O) OCH2CH2 - NHC(=O)-
CH2 =C( CH3 )C(=O) OCH2CH2 - NHC(=O)-
上記式(3)中、aは独立に2~5の整数であり、好ましくは2~4の整数であり、より好ましくは2又は3である。aが2未満では成分(C)に対する溶解性が低下する場合があり、5より大きいと成分(A)に対する溶解性が低下する場合がある。 In the above formula (3), a is independently an integer of 2-5, preferably an integer of 2-4, more preferably 2 or 3. If a is less than 2, the solubility in component (C) may be lowered, and if it is greater than 5, the solubility in component (A) may be lowered.
上記式(3)中、Q1は独立に少なくとも(a+1)個のケイ素原子を含む(a+1)価の連結基であり、環状構造をなしていてもよい。このようなQ1の好ましいものとして、それぞれ少なくとも(a+1)個のケイ素原子を有するシロキサン構造、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種以上の組み合わせからなる(a+1)価の連結基が挙げられる。このとき、(a+1)個の結合手は(a+1)個のケイ素原子をそれぞれ有することが好ましい。特に好ましい構造として、具体的には、下記の構造が示される。
但し、下記の構造において、aは上記式(3)のaと同じである。また、bは1~5の整数であり、好ましくは1~3の整数である。各ユニットの並びはランダムであり、(a+1)個の各ユニット等の結合手は、Z3及び[ ]で括られたa個のCH2のいずれかの基と結合する。In the above formula (3), Q 1 is independently a (a+1)-valent linking group containing at least (a+1) silicon atoms and may form a cyclic structure. Preferred examples of such Q 1 include a siloxane structure each having at least (a+1) silicon atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more of these (a+1) valent linking groups. At this time, the (a+1) bonds preferably each have (a+1) silicon atoms. As a particularly preferred structure, specifically, the following structure is shown.
However, in the structures below, a is the same as a in formula (3) above. Also, b is an integer of 1-5, preferably an integer of 1-3. The arrangement of each unit is random, and the bonds of each of the (a+1) units are bonded to any of Z 3 and a CH 2 groups enclosed in [ ].
ここで、T’は(a+1)価の連結基であり、例えば以下のものが例示される。
これらの中でも特に以下のものが好ましい。
上記式(3)中、Z2はそれぞれ独立に酸素原子及び/又は窒素原子を含んでいてもよい炭素数1~100、好ましくは炭素数1~40の2価の炭化水素基であり、途中環状構造を含んでいてもよい。In the above formula (3), Z 2 is each independently a divalent hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 40 carbon atoms, which may contain an oxygen atom and/or a nitrogen atom; It may contain a cyclic structure.
Z2の好ましい構造としては、以下のものを挙げることができる。
-CH2[OC2H4]d[OC3H6]e[OC4H8]fOCcH2c-
(式中、dは0~29の整数、好ましくは0~10の整数であり、eは0~29の整数、好ましくは0~10の整数であり、fは0~14の整数、好ましくは0~7の整数であり、cは2~4の整数である。上記構造の合計として炭素数3~100、好ましくは炭素数3~30を満たせばよい。繰り返し単位の配列は、種類にかかわらずランダムである。また各繰り返し単位は単体でなく構造異性体の混合物でもよい。)Preferred structures for Z 2 include the following.
-CH2 [ OC2H4 ] d [ OC3H6 ] e [ OC4H8 ] fOCcH2c-
(Wherein, d is an integer of 0 to 29, preferably an integer of 0 to 10, e is an integer of 0 to 29, preferably an integer of 0 to 10, f is an integer of 0 to 14, preferably It is an integer of 0 to 7, and c is an integer of 2 to 4. The total number of carbon atoms in the above structure may be 3 to 100, preferably 3 to 30. The arrangement of repeating units is independent of the type. Each repeating unit may be a mixture of structural isomers instead of a single unit.)
Z2として、特に好ましい構造としては、以下の2つのものが挙げられ、中でもdが0~10の整数、eが0~10の整数であるものが好適である。
-CH2[OC2H4]dOC2H4-
-CH2[OC3H6]eOCH2CH(CH3)-As Z 2 , particularly preferred structures include the following two structures, among which those in which d is an integer of 0-10 and e is an integer of 0-10 are preferred.
-CH2 [ OC2H4 ] dOC2H4- _
-CH2 [ OC3H6 ] eOCH2CH ( CH3 ) -
また、Z2としては、以下のような構造も挙げることができる。
上記式(3)中、Z3は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基からなる連結基であり、途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。このようなZ3として、好適な構造としては、以下に示す構造群が挙げられる。
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _
これらの中でも特に
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
が好ましい。Among these, -CH 2 CH 2 -
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _
is preferred.
上記式(3)で表される含フッ素アクリル化合物として、より好ましい構造としては、下記一般式(4)、(5)で表されるものが例示できる。
成分(B)として具体的には、下記に示すものが例示できる。
また、上記成分(B)の式(3)で表される含フッ素アクリル化合物は、例えば、特開2010-285501号公報、特開2015-199910号公報に示される方法により合成が可能である。 Further, the fluorine-containing acrylic compound represented by the formula (3) of the component (B) can be synthesized, for example, by the methods disclosed in JP-A-2010-285501 and JP-A-2015-199910.
例えば、上記式(3)で表される含フッ素アクリル化合物は、まず下記一般式(10)
で表される多官能Si-H基を有するフルオロポリエーテル化合物と、下記一般式(11)
CH2=CR1-Z2-OH (11)
(式中、R1、Z2は上記と同じである。)
で表される末端不飽和基含有アルコール(分子末端にアルケニル基と水酸基を有する化合物)とをヒドロシリル化反応させることにより、中間体である含フッ素アルコール化合物を得ることができる。For example, the fluorine-containing acrylic compound represented by the above formula (3) is first represented by the following general formula (10)
and a fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (11)
CH2 = CR1 - Z2 -OH (11)
(In the formula, R 1 and Z 2 are the same as above.)
A fluorine-containing alcohol compound, which is an intermediate, can be obtained by hydrosilylating a terminally unsaturated group-containing alcohol represented by (a compound having an alkenyl group and a hydroxyl group at the molecular terminal).
ここで、上記式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物としては、例えば、下記に示すものが例示できる。
また、上記式(11)で表される末端不飽和基含有アルコールとしては、下記に示すものが例示できる。
CH2=CH-CH2-OCH2CH2-OH
CH2=CH-CH2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH
CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH
CH2 =CH- CH2 -OCH2CH2 - OH
CH2 =CH- CH2 - OCH2CH ( CH3 )-OH
CH2 =CH- CH2- ( OC3H6 ) 2- OCH2CH ( CH3 ) -OH
CH2 = CH- CH2- ( OC3H6 ) 4- OCH2CH ( CH3 )-OH
CH2 =CH- CH2- ( OC3H6 ) 9- OCH2CH ( CH3 ) -OH
このヒドロシリル化(付加)反応は、式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物と、式(11)で表される末端不飽和基含有アルコールを混合し、白金族金属系の付加反応触媒存在下、反応温度50~150℃、好ましくは60~120℃で、1分~48時間、特に10分~12時間反応を行うことが望ましい。反応温度が低すぎると反応が十分に進行しないまま反応が停止してしまう場合があり、高すぎるとヒドロシリル化の反応熱による温度上昇で反応が制御できなくなり、突沸や原料の分解などが起こる場合がある。 In this hydrosilylation (addition) reaction, a fluoropolyether compound having a polyfunctional Si—H group represented by formula (10) and a terminal unsaturated group-containing alcohol represented by formula (11) are mixed, and platinum It is desirable to carry out the reaction at a reaction temperature of 50 to 150° C., preferably 60 to 120° C., for 1 minute to 48 hours, particularly 10 minutes to 12 hours, in the presence of a group metal-based addition reaction catalyst. If the reaction temperature is too low, the reaction may stop before the reaction proceeds sufficiently. If it is too high, the temperature rises due to the reaction heat of hydrosilylation, making the reaction uncontrollable and causing bumping or decomposition of the raw materials. There is
この場合、式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物と、式(11)で表される末端不飽和基含有アルコールとの反応割合は、式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物の[ ]で括られたHの総モル数に対して、式(11)で表される末端不飽和基含有アルコールの末端不飽和基を0.5~5倍モル、特に0.9~2倍モル使用して反応させることが望ましい。式(11)で表される末端不飽和基含有アルコールが、これより少なすぎると高い溶解性を持つ含フッ素アルコール化合物を得ることが困難となる場合があり、これ以上多すぎると反応溶液の均一性が低下して反応速度が不安定となり、また反応後に式(11)で表される末端不飽和基含有アルコールの除去を行う場合に加熱、減圧、抽出等の条件を余剰の未反応のアルコールが増える分だけ厳しくする必要が出てくる。 In this case, the reaction ratio between the fluoropolyether compound having a polyfunctional Si—H group represented by formula (10) and the terminal unsaturated group-containing alcohol represented by formula (11) is represented by formula (10). With respect to the total number of moles of H enclosed in [ ] of the fluoropolyether compound having a multifunctional Si—H group represented, the terminal unsaturated group-containing alcohol represented by the formula (11) is preferably used in an amount of 0.5 to 5 mol, particularly 0.9 to 2 mol, for the reaction. If the terminal unsaturated group-containing alcohol represented by formula (11) is too less than this, it may be difficult to obtain a highly soluble fluorine-containing alcohol compound. When removing the terminal unsaturated group-containing alcohol represented by the formula (11) after the reaction, conditions such as heating, reduced pressure, and extraction are changed so that excess unreacted alcohol It becomes necessary to make it stricter as much as .
付加反応触媒は、例えば、白金、ロジウム又はパラジウム等の白金族金属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。
付加反応触媒の配合量は、式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物に対し、含まれる金属量が0.1~5,000質量ppmとなる量であることが好ましく、より好ましくは0.2~1,000質量ppmとなる量である。The addition reaction catalyst can be, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium. Among them, compounds containing platinum are preferable, and hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, Alternatively, platinum supported on activated carbon can be used.
The amount of the addition reaction catalyst is such that the amount of metal contained is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a multifunctional Si—H group represented by formula (10). is preferable, and more preferably the amount is 0.2 to 1,000 ppm by mass.
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よい。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、反応後に生成する含フッ素アルコール化合物が、上記反応温度において可溶であるものが好ましい。このような溶剤としては、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。
溶剤を使用する場合、その使用量は、式(10)で表される多官能Si-H基を有するフルオロポリエーテル化合物100質量部に対して、好ましくは5~2,000質量部であり、より好ましくは50~500質量部である。これより少なければ溶剤による希釈の効果が薄くなり、多ければ希釈度が高くなりすぎて反応速度の低下を招く場合がある。The above addition reaction can be carried out without a solvent, but may be diluted with a solvent if necessary. At this time, as the diluent solvent, widely used organic solvents such as toluene, xylene and isooctane can be used. The fluoroalcohol compound is preferably soluble at the above reaction temperature. Examples of such solvents include fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and partially fluorine-modified solvents such as fluorine-modified ether solvents such as methyl perfluorobutyl ether. is desirable, and m-xylene hexafluoride is particularly preferred.
When using a solvent, the amount used is preferably 5 to 2,000 parts by mass with respect to 100 parts by mass of the fluoropolyether compound having a polyfunctional Si—H group represented by formula (10), More preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with the solvent will be weak, and if it is more than this, the degree of dilution will become too high, which may lead to a decrease in the reaction rate.
反応終了後、未反応の式(11)で表される末端不飽和基含有アルコールや希釈溶剤を減圧留去、抽出、吸着等の公知の方法で除去することが好ましいが、これらを含んだ反応混合物のまま次の反応に使用することもできる。 After completion of the reaction, the unreacted terminal unsaturated group-containing alcohol represented by formula (11) and the diluent solvent are preferably removed by a known method such as distillation under reduced pressure, extraction, or adsorption, but reactions involving these The mixture can also be used for the next reaction as it is.
このようにして得られる含フッ素アルコール化合物としては、下記に示すものが例示できる。
次いで、上記で得られた含フッ素アルコール化合物に(メタ)アクリル基を導入することにより、含フッ素アクリル化合物を得ることができる。含フッ素アルコール化合物に(メタ)アクリル基を導入する方法として、一つは下記式(12)で表される(メタ)アクリル酸ハライドと反応させてエステルを形成する方法、もう一つは下記式(13)で表される(メタ)アクリル基を含有するイソシアネート化合物と反応させる方法が挙げられ、これらの方法により、本発明の目的とする含フッ素アクリル化合物を得ることができる。 Then, by introducing a (meth)acryl group into the fluorine-containing alcohol compound obtained above, a fluorine-containing acrylic compound can be obtained. As a method for introducing a (meth)acrylic group into a fluorine-containing alcohol compound, one is a method of reacting with a (meth)acrylic acid halide represented by the following formula (12) to form an ester, and the other is a method of forming an ester by the following formula: A method of reacting with an isocyanate compound containing a (meth)acrylic group represented by (13) can be mentioned, and by these methods, the fluorine-containing acrylic compound aimed at by the present invention can be obtained.
CH2=CR3C(=O)X (12)
CH2=CR3C(=O)OCH2CH2-N=C=O (13)
(式中、R3、Xは上記と同じである。) CH2 = CR3C (=O)X (12)
CH2 = CR3C (=O) OCH2CH2 - N=C=O (13)
(In the formula, R 3 and X are the same as above.)
ここで、式(12)で表される(メタ)アクリル酸ハライドとしては、下記に示すものが挙げられる。
CH2=CHC(=O)X
CH2=C(CH3)C(=O)X
(式中、Xは上記と同じである。)
特にアクリル酸クロリド、メタクリル酸クロリドが好ましい。Here, examples of the (meth)acrylic acid halide represented by formula (12) include those shown below.
CH2 =CHC(=O)X
CH2 =C( CH3 )C(=O)X
(In the formula, X is the same as above.)
Acrylic acid chloride and methacrylic acid chloride are particularly preferred.
また、式(13)で表される(メタ)アクリル基を含有するイソシアネート化合物としては、下記に示すものが挙げられる。
CH2=CHC(=O)OCH2CH2-N=C=O
CH2=C(CH3)C(=O)OCH2CH2-N=C=OExamples of the (meth)acrylic group-containing isocyanate compound represented by formula (13) include those shown below.
CH2 =CHC(=O) OCH2CH2 - N=C=O
CH2 =C( CH3 )C(=O) OCH2CH2 - N=C=O
これらの(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物は、含フッ素アルコール化合物の水酸基量の合計に対して等モル以上を仕込み反応させ、水酸基をすべて反応させてもよいが、含フッ素アルコール化合物1モルに対して平均して1モル以上の(メタ)アクリル基を導入させればよく、水酸基を過剰とさせることで、未反応の(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物を残存させないようにしてもよい。具体的には、反応系中の含フッ素アルコール化合物量をxモル、含フッ素アルコール化合物の水酸基量の合計をyモルとした場合、(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物はxモル以上2yモル以下であることが望ましく、特に好ましくは0.6yモル以上1.4yモル以下である。少なすぎる場合、(メタ)アクリル基が全く導入されない含フッ素アルコール化合物が残存する可能性が高くなり、生成物の溶解性が低くなってしまう可能性がある。多すぎる場合、未反応の(メタ)アクリル酸ハライドあるいは(メタ)アクリル基を含有するイソシアネート化合物の残存の除去が困難となる。 These (meth)acrylic acid halides or (meth)acrylic group-containing isocyanate compounds may be reacted in an equimolar amount or more with respect to the total amount of hydroxyl groups in the fluorine-containing alcohol compound, and all the hydroxyl groups may be reacted. It suffices to introduce an average of 1 mol or more (meth)acrylic groups per 1 mol of the fluorine-containing alcohol compound. The isocyanate compound containing an acrylic group may not remain. Specifically, when the amount of fluorine-containing alcohol compound in the reaction system is x mol, and the total amount of hydroxyl groups of the fluorine-containing alcohol compound is y mol, (meth)acrylic acid halide or isocyanate containing (meth)acrylic group The amount of the compound is preferably x mol or more and 2 y mol or less, and particularly preferably 0.6 y mol or more and 1.4 y mol or less. If the amount is too small, there is a high possibility that the fluorine-containing alcohol compound in which no (meth)acrylic group is introduced remains, and the solubility of the product may become low. If the amount is too large, it becomes difficult to remove unreacted (meth)acrylic acid halides or residual isocyanate compounds containing (meth)acrylic groups.
これらの反応は、必要に応じて適当な溶剤で希釈して反応を行ってもよい。このような溶剤としては、含フッ素アルコール化合物の水酸基、(メタ)アクリル酸ハライドのハロゲン原子、(メタ)アクリル基を含有するイソシアネート化合物のイソシアネート基と反応しない溶剤であれば特に制限なく用いることができ、具体的には、トルエン、キシレン、イソオクタンなどの炭化水素系溶剤、THF、ジイソプロピルエーテル、ジブチルエーテル等のエーテル系溶剤、アセトン、メチルエチルケトン、メチルブチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、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などが挙げられる。この溶剤は、反応後に減圧留去等の公知の手法で除去してもよく、目的の用途に応じてそのまま希釈溶液として使用してもよい。
溶剤の使用量は特に限定されないが、反応成分の全合計質量に対して10倍以下が好ましい。溶剤の使用量が多すぎると、反応速度が大幅に低下する危険がある。These reactions may be carried out by diluting with a suitable solvent as necessary. As such a solvent, any solvent that does not react with the hydroxyl group of the fluorine-containing alcohol compound, the halogen atom of the (meth)acrylic acid halide, or the isocyanate group of the isocyanate compound containing the (meth)acrylic group can be used without particular limitation. Specifically, hydrocarbon solvents such as toluene, xylene and isooctane, ether solvents such as THF, diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone. , m-xylene hexafluoride, benzotrifluoride and other fluorine-modified aromatic hydrocarbon solvents, and methyl perfluorobutyl ether and other fluorine-modified ether solvents. This solvent may be removed by a known technique such as distillation under reduced pressure after the reaction, or may be used as it is as a diluted solution depending on the intended use.
The amount of the solvent to be used is not particularly limited, but is preferably 10 times or less with respect to the total mass of the reaction components. If too much solvent is used, there is a danger that the reaction rate will be greatly reduced.
また、反応の際には、必要に応じて重合禁止剤を添加してもよい。重合禁止剤としては特に制限はないが、通常、アクリル化合物の重合禁止剤として用いられるものを用いることができる。具体的には、ヒドロキノン、ヒドロキノンモノメチルエーテル、4-tert-ブチルカテコール、ジブチルヒドロキシトルエン等を挙げることができる。
重合禁止剤の使用量は反応条件、反応後の精製条件、最終的な使用条件から決定すればよく、特に制限はされないが、通常、反応成分の全合計質量に対して0.01~5,000ppm、特に好ましくは0.1~500ppmである。Moreover, you may add a polymerization inhibitor as needed in the case of reaction. The polymerization inhibitor is not particularly limited, but those commonly used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.
The amount of the polymerization inhibitor to be used may be determined based on the reaction conditions, post-reaction purification conditions, and final use conditions, and is not particularly limited, but is usually 0.01 to 5,000,000,000,000,000,000,000,000, or 000 ppm, particularly preferably 0.1 to 500 ppm.
含フッ素アルコール化合物に(メタ)アクリル酸ハライドを反応させる場合、特にアクリル酸クロリド、メタクリル酸クロリドを反応させて、エステルを生成することが好ましい。該エステル生成反応は、上記反応中間体(含フッ素アルコール化合物)、受酸剤を混合攪拌しながら(メタ)アクリル酸ハライドを滴下して行う。受酸剤はトリエチルアミン、ピリジン、尿素などが使用できる。受酸剤の使用量は、(メタ)アクリル酸ハライドの仕込みモル数に対して0.9~3倍程度が望ましい。少なすぎるとトラップされない酸が多く残存することになり、多すぎると余剰となる受酸剤の除去が困難になる。 When a (meth)acrylic acid halide is reacted with a fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride or methacrylic acid chloride to produce an ester. The ester formation reaction is carried out by dropping the (meth)acrylic acid halide while mixing and stirring the reaction intermediate (fluorine-containing alcohol compound) and the acid acceptor. Usable acid acceptors include triethylamine, pyridine, and urea. The amount of the acid acceptor used is desirably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. If it is too small, a large amount of untrapped acid will remain, and if it is too large, it will be difficult to remove the surplus acid acceptor.
(メタ)アクリル酸ハライドの滴下は、反応混合物の温度を0~35℃に維持し、20~60分かけて行う。その後、更に30分~10時間攪拌を継続する。反応終了後、未反応の(メタ)アクリル酸ハライド、反応により発生した塩及び反応溶剤等を留去、吸着、ろ過、洗浄等の方法で除去することで、上記式(3)で表される含フッ素アクリル化合物を得ることができる。 The dropwise addition of the (meth)acrylic acid halide is carried out over 20-60 minutes while maintaining the temperature of the reaction mixture at 0-35°C. Stirring is then continued for an additional 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, etc. are removed by a method such as distillation, adsorption, filtration, washing, etc., and the reaction represented by the above formula (3) is obtained. A fluorine-containing acrylic compound can be obtained.
また、反応停止の際に、メタノール、エタノール等のアルコール化合物を系内に添加し、未反応の(メタ)アクリル酸ハライドをエステル化してもよい。生成した(メタ)アクリル酸エステル類は、未反応の(メタ)アクリル酸ハライド除去と同様の方法で除去できるが、残存させたまま使用することもできる。 Moreover, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The (meth)acrylic acid esters produced can be removed by the same method as for removing unreacted (meth)acrylic acid halides, but they can also be used as they remain.
含フッ素アルコール化合物と(メタ)アクリル基を含有するイソシアネート化合物との反応の場合には、含フッ素アルコール化合物と(メタ)アクリル基を含有するイソシアネート化合物を必要に応じて溶剤とともに攪拌し、反応を進行させる。 In the case of the reaction between the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group, the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group are stirred together with a solvent if necessary to initiate the reaction. proceed.
この反応において、反応の速度を増加するために適切な触媒を加えてもよい。触媒としては、例えば、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジオクトエート、ジオクチル錫ジアセテート、ジオクチル錫ジラウレート、ジオクチル錫ジオクテート、ジオクタン酸第1錫などのアルキル錫エステル化合物、テトライソプロポキシチタン、テトラn-ブトキシチタン、テトラキス(2-エチルヘキソキシ)チタン、ジプロポキシビス(アセチルアセトナ)チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステル又はチタンキレート化合物、ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムモノブトキシアセチルアセトネートビス(エチルアセトアセテート)、ジルコニウムジブトキシビス(エチルアセトアセテート)、ジルコニウムテトラアセチルアセトネート、ジルコニウムキレート化合物等が例示される。これらはその1種に限定されず、2種もしくはそれ以上の混合物として使用できるが、特に環境への影響が低いチタン化合物や錫化合物の使用が好ましい。これらの触媒を反応物総質量に対して、0.01~2質量%、好ましくは0.05~1質量%加えることにより、反応速度を増加させることができる。 In this reaction, a suitable catalyst may be added to increase the rate of reaction. Examples of catalysts include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctoate, tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetona)titanium, titanium isopropoxyoctylene glycol, and other titanate esters or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxymonoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, zirconium chelate compounds and the like are exemplified. These compounds are not limited to one of them, and can be used as a mixture of two or more of them. Titanium compounds and tin compounds, which have a particularly low impact on the environment, are preferably used. The reaction rate can be increased by adding 0.01 to 2% by weight, preferably 0.05 to 1% by weight, of these catalysts relative to the total weight of the reactants.
上記反応は0~120℃、好ましくは10~70℃の温度で、1分~500時間、好ましくは10分~48時間行う。反応温度が低すぎると反応速度が遅くなりすぎる場合があり、反応温度が高すぎると副反応として(メタ)アクリル基の重合が起きてしまう可能性がある。 The above reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may become too slow, and if the reaction temperature is too high, polymerization of (meth)acrylic groups may occur as a side reaction.
反応終了後、未反応のイソシアネート化合物及び反応溶剤等を留去、吸着、ろ過、洗浄等の方法で除去することで、上記式(3)で表される含フッ素アクリル化合物を得ることができる。 After completion of the reaction, the unreacted isocyanate compound and reaction solvent are removed by distillation, adsorption, filtration, washing, or the like to obtain the fluorine-containing acrylic compound represented by the above formula (3).
また反応停止の際に、メタノール、エタノール等のアルコール化合物を系内に添加し、未反応のイソシアネート化合物とウレタン結合を形成させてもよい。生成したウレタンアクリレート類は、未反応のイソシアネート化合物と同様の方法で除去できるが、残存させたまま使用することもできる。 Also, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The produced urethane acrylates can be removed in the same manner as the unreacted isocyanate compound, but they can also be used as they remain.
〔成分(C)〕
本発明の含フッ素硬化性組成物における第三の必須成分である成分(C)は、フルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物である。成分(C)は、分子内にウレタン結合を有するウレタンアクリレート類や、各種重合体の側鎖や末端に任意の方法で2個以上の(メタ)アクリル基を導入した化合物も含む。[Component (C)]
Component (C), which is the third essential component in the fluorine-containing curable composition of the present invention, does not contain a fluoropolyether structure and has an average of two or more (meth)acrylic groups per molecule. It is a fluorinated acrylic compound. Component (C) also includes urethane acrylates having urethane bonds in the molecule, and compounds obtained by introducing two or more (meth)acryl groups to the side chains or terminals of various polymers by any method.
このような非フッ素化アクリル化合物(C)としては、1分子中に2個以上(メタ)アクリル基を有するものであればよく、例えば、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、アルキル変性品、エポキシ樹脂に(メタ)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、及び(メタ)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。 Such a non-fluorinated acrylic compound (C) may have two or more (meth)acrylic groups in one molecule, for example, 1,6-hexanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanurate ethylene oxide-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth) Acrylates, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, pentaerythritol Bi- to hexafunctional (meth)acrylics such as tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc. compounds, these (meth)acrylic compounds ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy acrylates obtained by adding (meth)acrylic acid to epoxy resins, and (meth)acrylic acid ester copolymers Examples include those containing a copolymer having a (meth)acryloyl group introduced into the side chain of the coalescence.
また、ウレタンアクリレート類、ポリイソシアネートに水酸基を有する(メタ)アクリレートを反応させて得られるもの、ポリイソシアネートと末端ジオールのポリエステルに水酸基を有する(メタ)アクリレートを反応させて得られるもの、ポリオールに過剰のジイソシアネートと反応させて得られるポリイソシアネートに、水酸基を有する(メタ)アクリレートを反応させて得られるものを使用することもできる。中でも、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシ-3-アクリロイロキシプロピルメタクリレート、及びペンタエリスリトールトリ(メタ)アクリレートから選ばれる水酸基を有する(メタ)アクリレートと、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート、リジンジイソシアネート、ノルボルナンジイソシアネート、1,3-ビス(イソシアナトメチル)シクロヘキサン、メチレンビス(4-シクロヘキシルイソシアネート)、2-メチル-1,3-ジイソシアナトシクロヘキサン、2-メチル-1,5-ジイソシアナトシクロヘキサン及びジフェニルメタンジイソシアネートから選ばれるポリイソシアネートを反応させたウレタンアクリレート類が好ましい。 In addition, urethane acrylates, those obtained by reacting polyisocyanate with a (meth)acrylate having a hydroxyl group, those obtained by reacting a polyisocyanate and a polyester with a terminal diol with a (meth)acrylate having a hydroxyl group, an excess of polyol It is also possible to use those obtained by reacting a polyisocyanate obtained by reacting the diisocyanate of (1) with a (meth)acrylate having a hydroxyl group. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and (meth)acrylate having a hydroxyl group selected from pentaerythritol tri(meth)acrylate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexylisocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5 - Urethane acrylates reacted with a polyisocyanate selected from diisocyanatocyclohexane and diphenylmethane diisocyanate are preferred.
成分(C)は、1種単独でも使用できるが、塗工性や硬化後被膜の特性を高めるために該当する複数の化合物を配合して使用することもできる。
特に1分子中に2個以上の(メタ)アクリル基を有し、ウレタン結合を有さない多官能アクリル化合物、又はこの多官能アクリル化合物と、脂肪族ポリイソシアネートと水酸基を有するアクリル化合物とを反応させて得られた1分子中に3個以上の(メタ)アクリル基を有する多官能ウレタンアクリレート類からなるものとを含む少なくとも2種類のアクリル化合物の混合物を用いることが好ましい。Component (C) can be used alone, but can also be used by blending a plurality of corresponding compounds in order to improve coatability and properties of the cured film.
In particular, a polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and no urethane bond, or reacting this polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group It is preferable to use a mixture of at least two kinds of acrylic compounds, including polyfunctional urethane acrylates having 3 or more (meth)acrylic groups in one molecule, which are obtained by the following methods.
ここで、1分子中に2個以上の(メタ)アクリル基を有し、ウレタン結合を有さない多官能アクリル化合物としては、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、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、及びこれらをエチレンオキサイド又はプロピレンオキシドで変性させた化合物が挙げられる。 Here, polyfunctional acrylic compounds having two or more (meth)acrylic groups in one molecule and no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and Compounds obtained by modifying these with ethylene oxide or propylene oxide are exemplified.
脂肪族ポリイソシアネートと水酸基を有するアクリル化合物とを反応させて得られた1分子中に3個以上の(メタ)アクリル基を有する多官能ウレタンアクリレート類としては、ヘキサメチレンジイソシアネート、ノルボルナンジイソシアネート、イソホロンジイソシアネート及びこれらの3量化物及び、これらの2官能、3官能のイソシアネート類に脂肪族ジオール、脂肪族ポリオール及び側鎖に水酸基を有するポリアクリレート類と反応させて得られる2官能以上のポリイソシアネートに、トリメチロールプロパンジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、ビス(2-(メタ)アクリロイルオキシエチル)ヒドロキシエチルイソシアヌレート、ペンタエリスリトールトリ(メタ)アクリレート、ジトリメチロールプロパントリ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート及びこれらのエチレンオキサイド、プロピレンオキサイド変性体を反応させたものや、脂肪族ポリオール及び側鎖に水酸基を有するポリアクリレート類と2-イソシアナトエチル(メタ)アクリラートや1,1-(ビスアクリロイルオキシメチル)エチルイソシアネート等のイソシアネート基を有するアクリル化合物を反応させたものを示すことができる。 Polyfunctional urethane acrylates having 3 or more (meth)acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate. And these trimers and bifunctional or trifunctional isocyanates are reacted with aliphatic diols, aliphatic polyols and polyacrylates having hydroxyl groups in side chains to bifunctional or higher polyisocyanates, Trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, di Pentaerythritol penta (meth) acrylate and those obtained by reacting ethylene oxide and propylene oxide modified products thereof, aliphatic polyols and polyacrylates having hydroxyl groups in side chains and 2-isocyanatoethyl (meth) acrylate, 1, It can be obtained by reacting an acrylic compound having an isocyanate group such as 1-(bisacryloyloxymethyl)ethyl isocyanate.
また、成分(C)としては、液状の成分だけでなく、微粒子状の高分子量体の表面や無機フィラー微粒子の表面を(メタ)アクリル基で修飾したものを含んでいてもよい。 In addition, the component (C) may include not only a liquid component but also those obtained by modifying the surface of fine particles of a high molecular weight substance or inorganic filler fine particles with a (meth)acrylic group.
本発明の含フッ素硬化性組成物においては、各成分の組成比率は成分(C)100質量部に対して、成分(A)と成分(B)の配合量の合計が0.05~50質量部、特に好ましくは0.1~10質量部であり、かつ成分(B)100質量部に対する成分(A)の配合量が1~100質量部、特に好ましくは3~50質量部の範囲内にあることが望ましい。成分(C)に対して成分(A)、(B)の合計がこれより多すぎると、ハードコート被膜としての性能が低下し、少なすぎると十分な防汚性能を発揮できない。成分(B)に対して成分(A)の量がこれより多すぎると、成分(C)に対する溶解性が悪くなりすぎて塗工不良が発生するおそれがあり、少なすぎると成分(B)単独での使用に対しての差がみられなくなる。 In the fluorine-containing curable composition of the present invention, the composition ratio of each component is 0.05 to 50 mass parts of component (A) and component (B) per 100 mass parts of component (C). part, particularly preferably 0.1 to 10 parts by mass, and the amount of component (A) blended with respect to 100 parts by mass of component (B) is 1 to 100 parts by mass, particularly preferably 3 to 50 parts by mass. It is desirable to have If the total amount of components (A) and (B) is too large relative to component (C), the performance of the hard coat film will deteriorate, and if it is too small, sufficient antifouling performance cannot be exhibited. If the amount of component (A) is too large relative to component (B), the solubility in component (C) may become too poor, resulting in poor coating. No difference can be seen for use in
本発明の含フッ素硬化性組成物は、上述した成分(A)、(B)、(C)の3種の成分を必須とし、これらのみを配合したものを熱、電子線等で硬化させることもできるが、作業性や必要に応じてこれら3成分以外の成分を含有することもできる。
特に成分(D)として光重合開始剤を含有することで、活性エネルギー線として紫外線を用いた場合の硬化性を高めた硬化性組成物とすることができる。The fluorine-containing curable composition of the present invention essentially comprises the above-described three components (A), (B), and (C), and a mixture of these components alone is cured by heat, electron beams, or the like. However, it is also possible to contain components other than these three components depending on workability and necessity.
In particular, by containing a photopolymerization initiator as component (D), it is possible to obtain a curable composition having enhanced curability when ultraviolet rays are used as active energy rays.
〔成分(D)〕
成分(D)の光重合開始剤は、紫外線照射によりアクリル化合物を硬化させることができるものであれば特に限定されないが、好ましくは、例えば、アセトフェノン、ベンゾフェノン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシシクロヘキシル-フェニル-ケトン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)]、エタノン-1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-1-(O-アセチルオキシム)、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン等が挙げられ、1種単独でも2種以上を併用してもよい。[Component (D)]
The photopolymerization initiator of component (D) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, but preferably includes, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2 -hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4 ,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O- benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4- [4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, etc., may be used alone or in combination of two or more.
成分(D)の含有量は、硬化条件と目的とする該組成物の物性に応じて適宜決めることができるが、例えば成分(C)100質量部に対して、0.1~15質量部、特に1~10質量部となる量であることが望ましい。添加量がこれより少ないと硬化性が低下する場合があり、これより多くなると硬化後の物性への影響が大きくなるおそれがある。 The content of component (D) can be appropriately determined according to the curing conditions and the desired physical properties of the composition. In particular, it is desirable that the amount is 1 to 10 parts by mass. If the amount added is less than this, the curability may be lowered, and if the amount is more than this, there is a risk that the physical properties after curing will be greatly affected.
これら成分(A)、(B)、(C)、(D)は、それぞれの化合物の定義において構造が該当する一種類の化合物あるいは複数化合物の混合物として使用することができる。複数の化合物の混合物である場合、配合量を考えるには各化合物群の総質量をそれぞれの質量と考えればよい。 These components (A), (B), (C), and (D) can be used as a single type of compound or a mixture of multiple compounds whose structure corresponds to the definition of each compound. In the case of a mixture of a plurality of compounds, the total mass of each compound group should be considered as the mass of each compound when considering the blending amount.
本発明の含フッ素硬化性組成物には、更に、目的に応じて、反応性希釈剤としての1官能アクリル化合物、チオール化合物やマレイミド化合物など、(メタ)アクリル基以外の活性エネルギー線反応性化合物、有機溶剤、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及び高分子や無機物のフィラー等を配合することもできる。 The fluorine-containing curable composition of the present invention may further contain active energy ray-reactive compounds other than (meth)acrylic groups, such as monofunctional acrylic compounds, thiol compounds, and maleimide compounds, as reactive diluents, depending on the purpose. , organic solvents, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and polymer and inorganic fillers. can also
有機溶剤としては、1-プロパノール、2-プロパノール、イソプロピルアルコール、n-ブタノール、イソブタノール、tert-ブタノール、ジアセトンアルコールなどのアルコール類;メチルプロピルケトン、ジエチルケトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類;ジプロピルエーテル、ジブチルエーテル、アニソール、ジオキサン、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテートなどのエーテル類;酢酸プロピル、酢酸ブチル、酢酸シクロヘキシルなどのエステル類、トルエン、キシレン、トリエチルベンゼン、アルキルベンゼン類の芳香族類などを挙げることができる。上記溶剤は、1種を単独で用いてもよいし、2種以上を混合して用いてもよい。
溶剤の使用量は特に制限されるものではないが、成分(A)~(C)の合計100質量部に対し、20~10,000質量部が好ましく、特に100~1,000質量部が好ましい。Organic solvents include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol and diacetone alcohol; methylpropylketone, diethylketone, methylethylketone, methylisobutylketone, cyclohexanone and the like. ketones; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; propyl acetate, butyl acetate, cyclohexyl acetate, etc. and aromatics such as toluene, xylene, triethylbenzene and alkylbenzenes. The above solvents may be used singly or in combination of two or more.
The amount of the solvent used is not particularly limited, but is preferably 20 to 10,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass of components (A) to (C) in total. .
また、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及びフィラーとしては特に制限されず、公知のものを本発明の目的を損なわない範囲で使用することができる。 In addition, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers are not particularly limited, and known ones can be used. It can be used as long as the object of the present invention is not impaired.
更に、本発明の目的と効果を阻害しない範囲内においては本発明における成分(A)、(B)を製造するにあたって発生する副生成物、残存する未反応成分等を含んでいてもよい。このような成分としては、例えば上述した式(6)、(7)で表される含フッ素アルコール化合物が未反応成分として残留した場合などが考えられる。 Furthermore, it may contain by-products generated in the production of the components (A) and (B) in the present invention, residual unreacted components, etc., as long as they do not impair the object and effect of the present invention. As such a component, for example, the fluorine-containing alcohol compounds represented by the formulas (6) and (7) may remain as unreacted components.
なお、成分(C)及び各種添加物が配合されたハードコート剤は、各社からさまざまなものが市販されている。本発明の含フッ素硬化性組成物は、このような市販品のハードコート剤に成分(A)と成分(B)を添加したものであってもよい。市販品のハードコート剤として、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」等が挙げられる。 Various hard coating agents containing the component (C) and various additives are commercially available from various companies. The fluorine-containing curable composition of the present invention may be obtained by adding component (A) and component (B) to such a commercially available hard coating agent. Commercially available hard coating agents include, for example, Arakawa Chemical Industries Co., Ltd. "Beam Set", Ohashi Chemical Industry Co., Ltd. "Ubik", Origin Electric Co., Ltd. "UV Coat", Cashew Co., Ltd. "Cashew UV", JSR Corporation "Desolite", Dainichiseika Kogyo Co., Ltd. "Seika Beam", Nippon Synthetic Chemical Co., Ltd. "Shiko", Fujikura Kasei Co., Ltd. "Fuji Hard", Mitsubishi Rayon Co., Ltd. "Diabeam", Musashi Paint Co., Ltd. "Ultrabine" etc. are mentioned.
また、上記のように市販品のハードコート剤を用いる場合であっても、目的に応じて、有機溶剤、重合禁止剤、帯電防止剤、消泡剤、粘度調整剤、耐光安定剤、耐熱安定剤、酸化防止剤、界面活性剤、着色剤、及びフィラー等を追加して配合することができる。 In addition, even if a commercially available hard coating agent is used as described above, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, and a heat stabilizer may be used depending on the purpose. Agents, antioxidants, surfactants, colorants, fillers, and the like can be additionally incorporated.
以上のような成分(C)、(D)、及びその他任意に配合可能な添加剤については、例えばテクノネット社編「光硬化技術データブック 材料編」(2000年、テクノネット社)、フォトポリマー懇話会編「フォトポリマーハンドブック」(1989年、工業調査会)、総合技術センター編「UV・EB硬化技術」(1982年、総合技術センター)、ラドテック研究会編「UV・EB硬化材料」(1992年、シーエムシー)、技術情報協会編「UV硬化における硬化不良・阻害原因とその対策」(2003年、技術情報協会)、技術情報協会編「UV硬化樹脂の配合設計、特性評価と新しい応用」(2017年、技術情報協会)、シーエムシー出版編「UV・EB硬化材料・製品の市場実態と展望」(2007年、シーエムシー出版)、サイエンス&テクノロジー編「UV硬化プロセスの最適化」(2008年、サイエンス&テクノロジー)等に公知のものが多く示されており、これらを任意の組み合わせで使用できる。 Components (C) and (D) as described above, and other additives that can be arbitrarily blended, are described, for example, by Technonet Co., Ltd., "Light Curing Technology Data Book, Material Edition" (2000, Technonet Co.), Photopolymer Konwakai ed. "Photopolymer Handbook" (1989, Industrial Research Institute), Sogo Gijutsu Center ed. 2003, CMC), Technical Information Institute, "Cure Defective/Inhibition Causes and Countermeasures in UV Curing" (2003, Technical Information Institute), Technical Information Institute, "Composition Design, Characteristic Evaluation and New Applications of UV Curing Resins". (Technical Information Association, 2017), CMC Publishing, "Market Status and Prospects for UV/EB Curing Materials and Products" (2007, CMC Publishing), Science & Technology, "Optimization of UV Curing Process" (2008) , Science & Technology), etc., and these can be used in any combination.
本発明の含フッ素硬化性組成物の配合方法については用途に応じて任意の方法で行えばよく、特に制限はされないが、他の成分と混合させる前に成分(A)と成分(B)が良く混合されていることが望ましく、例えば成分(A)と成分(B)を必要とする比率で混合し必要に応じて溶剤で希釈したものを成分(C)及びその他の成分と混合する、あるいは溶剤で希釈された成分(A)と溶剤で希釈された成分(B)を混合して成分(C)及びその他の成分と混合する方法などが好適である。 The method of blending the fluorine-containing curable composition of the present invention may be any method depending on the application, and is not particularly limited. It is desirable to be well mixed, for example, components (A) and (B) are mixed in the required ratio, diluted with a solvent if necessary, and then mixed with component (C) and other components, or A method of mixing the component (A) diluted with a solvent and the component (B) diluted with a solvent and mixing with the component (C) and other components is suitable.
本発明の含フッ素硬化性組成物の硬化方法は特に限定されず、成分(A)、(B)、(C)を含む組成物を、適宜溶剤で希釈、塗布したものを熱や電子線等の活性エネルギー線によって硬化させることもできるが、更に成分(D)の光重合開始剤を含有する場合は、紫外線によって硬化させることができる。紫外線による硬化の場合、紫外線照射を空気中で行うこともできるが、酸素による硬化阻害を防止するため酸素濃度を5,000ppm以下に抑えることが好ましく、窒素、二酸化炭素、アルゴン等の不活性ガス雰囲気下で硬化させることが特に好ましい。 The method of curing the fluorine-containing curable composition of the present invention is not particularly limited. However, when the photopolymerization initiator of component (D) is further contained, it can be cured with ultraviolet rays. In the case of curing with ultraviolet rays, ultraviolet irradiation can be performed in the air, but it is preferable to suppress the oxygen concentration to 5,000 ppm or less in order to prevent inhibition of curing by oxygen, and inert gases such as nitrogen, carbon dioxide, and argon. Curing under atmosphere is particularly preferred.
また、本発明の含フッ素硬化性組成物の一般的な使用形態としては、本発明の含フッ素硬化性組成物層が硬化後に密着又は接着するものであればいかなる基材上に塗布することもできるが、特に樹脂基材、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリエチレン、ポリプロピレン、セロファン、ジアセチルセルロース、トリアセチルセルロース、アセチルセルロースブチレート、セルロースアセテートプロピオネート、シクロオレフィンポリマー、シクロオレフィンコポリマー、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、エチレン-酢酸ビニル共重合体、ポリスチレン、ポリカーボネート、ポリメチルペンテン、ポリスルホン、ポリエーテルエーテルケトン、ポリエーテルスルホン、ポリエーテルイミド、ポリイミド、フッ素樹脂、ナイロン、アクリル樹脂等の樹脂を挙げることができる。これらは、フィルム、板状、及び成形部材等任意の形態をとるものに対してその表面に使用できる。 Further, as a general form of use of the fluorine-containing curable composition of the present invention, the fluorine-containing curable composition layer of the present invention may be applied onto any substrate as long as it adheres or adheres after curing. can, but especially resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymers, cyclo Olefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluorine resin, Resins such as nylon and acrylic resins can be used. They can be used on the surfaces of films, plates, and moldings of any shape.
またフィルム基材に塗工した場合、含フッ素硬化性組成物層を塗布・形成したのと反対の面に粘着剤を塗布した構造をとっていてもよく、更に粘着剤を保護するための離型フィルムを配置してもよい。 In the case of coating on a film base material, it may have a structure in which an adhesive is applied to the opposite side of the fluorine-containing curable composition layer coated and formed. A mold film may be placed.
また、前記フィルム基材は、上記で挙げた樹脂フィルムのみからなる基材であってもよいが、本発明の含フッ素硬化性組成物との密着性を向上させるために、前記樹脂フィルムにプライマー層を設けたフィルム基材であってもよい。前記プライマー層としては、例えば、ポリエステル系樹脂、ウレタン系樹脂、アクリル系樹脂等からなるものが挙げられる。 Further, the film substrate may be a substrate consisting of only the above-mentioned resin film. It may be a film substrate provided with a layer. Examples of the primer layer include those made of polyester-based resins, urethane-based resins, acrylic-based resins, and the like.
また本発明の含フッ素硬化性組成物は、硬化・未硬化の本発明に該当しない硬化性組成物層上に塗工硬化してもよい。例えば、硬度、耐久性、帯電防止性、カールなどの変形防止性がより高い硬化物層の上に本発明の含フッ素硬化性組成物を重ね塗りすることができる。 The fluorine-containing curable composition of the present invention may be coated and cured on a cured or uncured curable composition layer that does not correspond to the present invention. For example, the fluorine-containing curable composition of the present invention can be overcoated on a cured product layer having higher hardness, durability, antistatic properties, and anti-curling properties.
また、本発明の含フッ素硬化性組成物との密着性を向上させる目的で、樹脂基材表面を、サンドブラスト法、溶剤処理法等による表面の凹凸化処理、コロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線照射処理、酸化処理等により処理を施すこともできる。 For the purpose of improving the adhesion with the fluorine-containing curable composition of the present invention, the surface of the resin substrate may be subjected to roughening treatment such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, and flame treatment. Treatment, hot air treatment, ozone/ultraviolet irradiation treatment, oxidation treatment, or the like can also be applied.
本発明の含フッ素硬化性組成物を上記基材や物品に塗布する方法としては、特に制限はされないが、例えば、ロールコート、グラビアコート、フローコート、カーテンコート、ディップコート、スプレーコート、スピンコート、バーコート、スクリーン印刷等の公知の塗工方法を用いることができる。 The method of applying the fluorine-containing curable composition of the present invention to the substrate or article is not particularly limited, but examples include roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, and spin coating. , bar coating, screen printing, and other known coating methods can be used.
塗工後、塗膜に活性エネルギー線を照射してこれを硬化させる。ここで、活性エネルギー線としては、電子線、紫外線等任意のものを用いることができるが、特に紫外線が好ましい。紫外線源としては、水銀ランプ、メタルハライドランプ、LEDランプが好適である。紫外線照射量としては、少なすぎると未硬化成分が残存し、多すぎると塗膜及び基材が劣化する可能性があるため、10~10,000mJ/cm2、特に100~4,000mJ/cm2の範囲にあることが望ましい。After coating, the coating film is irradiated with active energy rays to cure it. Here, as the active energy ray, an electron beam, ultraviolet rays, or any other rays can be used, but ultraviolet rays are particularly preferable. Mercury lamps, metal halide lamps, and LED lamps are suitable as ultraviolet light sources. The amount of UV irradiation is 10 to 10,000 mJ/ cm.sup.2 , especially 100 to 4,000 mJ/cm. It is desirable to be in the range of 2 .
また酸素による硬化阻害を防止するために、紫外線照射時に照射雰囲気を窒素、二酸化炭素、アルゴン等の酸素分子を含まない不活性ガスで置換したり、塗膜表面を離型性を持つ紫外線透過性のある保護層で覆い、その上から紫外線を照射したり、基材が紫外線透過性を有する場合は塗膜表面を離型性のある保護層で覆った上で基材の塗工面とは反対側から紫外線を照射してもよい。また塗膜のレベリングあるいは塗膜中の(メタ)アクリル基の重合を効果的に行うため、紫外線照射前及び照射中に塗膜及び基材を赤外線や熱風乾燥炉等任意の手法で加熱してもよい。 In addition, in order to prevent curing inhibition due to oxygen, the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, argon, etc. during ultraviolet irradiation, and the coating film surface is treated with a UV-transmitting agent that has releasability. Cover with a protective layer and irradiate UV rays from above, or if the substrate has UV transparency, cover the coating surface with a protective layer that has releasability and then place it on the opposite side of the coated surface of the substrate You may irradiate an ultraviolet-ray from the side. In order to level the coating film or to effectively polymerize the (meth)acrylic groups in the coating film, the coating film and substrate are heated by any method such as infrared rays or a hot air drying furnace before and during UV irradiation. good too.
このようにして得られる含フッ素硬化性組成物の硬化物層の厚みとしては特に制限されないが、0.01~5,000μm、特に0.05~200μmであることが好ましい。 The thickness of the cured product layer of the fluorine-containing curable composition thus obtained is not particularly limited, but is preferably 0.01 to 5,000 μm, particularly 0.05 to 200 μm.
また、このようにして得られる本発明の含フッ素硬化性組成物の硬化物層は、イオン交換水の2μLの液滴が接液から1秒後に液面と固体面とのなす角により測定した静的水接触角が114°以上、特に115°以上、オレイン酸の4μLの液滴が接液から1秒後に液面と固体面とのなす角により測定した静的オレイン酸接触角が73°以上、特に74°以上である撥水撥油性表面となり得ることが好ましい。また、本発明の含フッ素硬化性組成物の硬化物層は、硬化被膜の動摩擦係数が0.10以下、特に0.09以下である低い動摩擦係数を有する撥水撥油性表面となり得ることが好ましい。なお、上記接触角及び/又は動摩擦係数とするためには、本発明の含フッ素硬化性組成物の硬化物層が、該硬化物層の全表面積に対して平均して厚さ10nm以上の層をなせる量であることが好ましい。また、硬化物層表面には未反応の(メタ)アクリル基が残存していないほど好ましく、このため窒素、二酸化炭素等の不活性ガス雰囲気下で硬化させた硬化物層であることが望ましい。 The cured product layer of the fluorine-containing curable composition of the present invention obtained in this manner was measured by measuring the angle formed by the liquid surface and the solid surface one second after contact with a 2 μL droplet of ion-exchanged water. A static water contact angle of 114° or more, particularly 115° or more, and a static oleic acid contact angle of 73° measured by the angle formed by the liquid surface and the solid surface one second after a 4 μL droplet of oleic acid comes into contact with the liquid. It is preferable to be able to have a water- and oil-repellent surface having an angle of 74° or more, particularly 74° or more. In addition, the cured product layer of the fluorine-containing curable composition of the present invention preferably has a water-repellent and oil-repellent surface with a low dynamic friction coefficient of 0.10 or less, particularly 0.09 or less. . In order to achieve the above contact angle and/or dynamic friction coefficient, the cured product layer of the fluorine-containing curable composition of the present invention must have an average thickness of 10 nm or more with respect to the total surface area of the cured product layer. It is preferable that it is an amount that can be made. In addition, it is preferable that no unreacted (meth)acrylic groups remain on the surface of the cured product layer. Therefore, it is preferable that the cured product layer is cured in an atmosphere of an inert gas such as nitrogen or carbon dioxide.
以上のように、本発明の含フッ素硬化性組成物は、紫外線等の活性エネルギー線によって硬化可能であり、物品の表面に、撥水撥油性、防汚性、滑り性、耐摩耗性に優れた硬化樹脂層を形成することができる。 As described above, the fluorine-containing curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and is excellent in water and oil repellency, antifouling properties, slipperiness and wear resistance on the surface of articles. A hardened resin layer can be formed.
更に、本発明では、上述した本発明の含フッ素硬化性組成物を表面に塗布し硬化させた硬化被膜を有する物品を提供する。上述したように、本発明の含フッ素硬化性組成物を用いれば、基材(物品)の表面に優れた表面特性を有する硬化被膜(硬化樹脂層)を形成することが可能になる。特に、アクリルハードコートの表面に撥水性、撥油性、防汚性を付与するのに有用である。これによって、指紋、皮脂、汗などの人脂、化粧品等による汚れ、機械油などが付着し難くなり、かつ拭き取り性にも優れたハードコート表面を基材に与えることができる。このため、本発明の含フッ素硬化性組成物は、人が触れて人脂、化粧品等により汚される可能性のある基材(物品)、また作業者の人脂や機械油などで汚染される可能性のある機械内部に用いられる工程材料フィルム等の表面に対する防汚塗装膜もしくは保護膜を提供することができる。 Furthermore, the present invention provides an article having a cured film obtained by coating the surface of the fluorine-containing curable composition of the present invention and curing the composition. As described above, by using the fluorine-containing curable composition of the present invention, it is possible to form a cured film (cured resin layer) having excellent surface properties on the surface of a substrate (article). In particular, it is useful for imparting water repellency, oil repellency, and antifouling properties to the surface of an acrylic hard coat. As a result, fingerprints, sebum, human oils such as perspiration, dirt from cosmetics, etc., and machine oil are less likely to adhere, and a hard coat surface excellent in wiping properties can be provided to the substrate. For this reason, the fluorine-containing curable composition of the present invention is a substrate (article) that may be soiled by human oils, cosmetics, etc., when touched by a person, or may be soiled by workers' human oils, machine oils, etc. An antifouling coating or protective coating can be provided for surfaces such as process material films that are potentially used inside machinery.
本発明の含フッ素硬化性組成物を用いて形成される硬化被膜(硬化樹脂層)は、タブレット型コンピュータ、ノートPC、携帯電話・スマートフォン等の携帯(通信)情報端末、デジタルメディアプレイヤー、電子ブックリーダーなど各種機器の筐体、時計型・眼鏡型ウェアラブルコンピュータ、ヘッドマウントディスプレイ、液晶ディスプレイ、プラズマディスプレイ、有機EL(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、CRT、トナー系ディスプレイ、量子ドット(QD)ディスプレイなどの各種フラットパネルディスプレイ及びTVの画面などの表示操作機器表面及びこれらの内部に使用される各種光学フィルム類、自動車の外装、ピアノや家具の光沢表面、大理石等の建築用石材表面、トイレ、風呂、洗面所等の水周りの装飾建材、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、フォトフレーム用カバー、腕時計、化粧品容器の外装、装飾品容器の外装、自動車窓用ガラス、列車、航空機等の窓ガラス、自動車ヘッドライト、テールランプなどの透明なガラス製又は透明なプラスチック製(アクリル、ポリカーボネートなど)部材、ミリ波レーダー等の車用センサーのカバー部材、各種ミラー部材等の塗装膜及び表面保護膜として有用である。 The cured film (cured resin layer) formed using the fluorine-containing curable composition of the present invention can be used for tablet computers, notebook PCs, portable (communication) information terminals such as mobile phones and smart phones, digital media players, and electronic books. Casings for various devices such as readers, watch-type/glass-type wearable computers, head-mounted displays, liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, vacuum fluorescent display (VFD), field emission projection displays , CRT, toner-based displays, quantum dot (QD) displays and other flat panel displays, TV screens and other display operation device surfaces and various optical films used inside these, automobile exteriors, pianos and furniture Glossy surfaces, architectural stone surfaces such as marble, decorative building materials around water such as toilets, baths, washrooms, etc. Protective glass for displaying works of art, show windows, showcases, covers for photo frames, watches, exteriors and decorations for cosmetic containers Exterior of product containers, window glass for automobiles, window glass for trains, aircraft, etc., transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as automobile headlights and tail lamps, automotive sensors such as millimeter wave radar It is useful as a coating film and a surface protective film for cover members of various mirror members.
中でも特に、タッチパネルディスプレイなど人の指あるいは手のひらで画面上の操作を行う表示入力装置を有する各種機器、例えば、タブレット型コンピュータ、ノートPC、スマートフォン、携帯電話、その他携帯(通信)情報端末、スマートウォッチ、デジタルメディアプレイヤー、電子ブックリーダー、デジタルフォトフレーム、ゲーム機、デジタルカメラ、デジタルビデオカメラ、GPS表示記録機器、自動車用等のナビゲーション装置、自動車用等の制御パネル、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、デジタルサイネージ(電子看板)、セキュリティーシステム端末、POS端末、リモートコントローラなど各種コントローラ、車載装置用パネルスイッチなどの表示入力装置などの表面保護膜として有用である。 In particular, various devices having a display input device such as a touch panel display for operating on the screen with a human finger or palm, such as tablet computers, notebook PCs, smartphones, mobile phones, other mobile (communication) information terminals, smart watches , Digital Media Players, Electronic Book Readers, Digital Photo Frames, Game Machines, Digital Cameras, Digital Video Cameras, GPS Display Recording Devices, Navigation Devices for Automobiles, etc., Control Panels for Automobiles, etc., Automatic Cash Drawer and Deposit Equipment, Cash Automatic It is useful as a surface protective film for payment machines, vending machines, digital signage (electronic signboards), security system terminals, POS terminals, various controllers such as remote controllers, and display input devices such as panel switches for in-vehicle devices.
更に本発明の含フッ素硬化性組成物により形成される硬化被膜は、光磁気ディスク、光ディスク等の光記録媒体;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、各種カメラ用レンズ、各種レンズ用保護フィルター、光ファイバーや光カプラーなどの光学部品・光デバイスの表面保護被膜としても有用である。 Further, the cured film formed from the fluorine-containing curable composition of the present invention can be used for optical recording media such as magneto-optical discs and optical discs; It is also useful as a surface protective film for lenses, antireflection films, various camera lenses, protective filters for various lenses, and optical parts and optical devices such as optical fibers and optical couplers.
以上のような、本発明の含フッ素硬化性組成物は、目的とする物品の表面に本発明に係る成分(A)、(B)の化合物中のフルオロポリエーテル構造を配置させることにより、撥水性、撥油性、滑り性、防汚性、指紋の目立ちにくさ、指紋拭き取り性、耐摩耗性、低屈折率特性、耐溶剤性、耐薬品性等の優れた性質を与えることをその本質としている。 As described above, the fluorine-containing curable composition of the present invention can be repelled by disposing the fluoropolyether structure in the compounds of the components (A) and (B) according to the present invention on the surface of the target article. The essence is to provide excellent properties such as water resistance, oil repellency, slipperiness, antifouling properties, inconspicuous fingerprints, fingerprint wiping properties, abrasion resistance, low refractive index properties, solvent resistance, and chemical resistance. there is
このような本発明の含フッ素硬化性組成物を使用する際は、配合物の組み合わせ、組成比、どのような特性を重視するかに応じて、適切な使用方法をそれぞれの用途に応じた公知の技術を元に選定すればよい。このような公知の技術は、フッ素を含む組成物に対するものだけでなく、既存の活性エネルギー線硬化性組成物に用いられている手法を含めて検討の範囲に含めることができる。 When using such a fluorine-containing curable composition of the present invention, an appropriate usage method is known according to each application, depending on the combination of compounds, composition ratio, and what kind of characteristics are emphasized. can be selected based on the technology of Such known techniques can be included in the scope of examination including not only those for fluorine-containing compositions, but also methods used for existing active energy ray-curable compositions.
例えば、本発明の含フッ素硬化性組成物を配合調製する際に、本発明に係る成分(A)、(B)に加えて、前記した本含フッ素硬化性組成物における各種配合物を組み合わせる際に、低屈折率特性やこれを利用した低反射特性を重視する場合には、反応性中空シリカや反応性基を有しない中空シリカ、あるいは成分(C)として特に3官能以上の非フッ素系の多官能アクリル化合物を使用すること、また被膜強度や耐擦傷性を向上させる場合には、成分(C)として2種類以上の非フッ素系多官能アクリル化合物を好適な量に配合すること、あるいは硬度と屈曲性のバランスをとるためには、成分(C)として非フッ素系の6官能以上の多官能アクリル化合物と3官能以下のアクリル化合物の組み合わせを行うこと等は、公知のアクリル硬化性組成物配合の知見から容易に類推できる。
また、本発明の含フッ素硬化性組成物を塗布することで物品を得る場合、例えば、フィルム基材への塗工を行う際、干渉縞を防ぐために適切な塗工膜厚となるように調整を行うこと、フィルム基材の厚さを調整してカールを抑制しやすくしたり、基材フィルムの弾性率を調整したりすることで含フッ素硬化性組成物の塗膜硬化後の変形や塗膜の割れを抑制すること等は、それぞれの特性に応じた既存の条件の組み合わせを元にスクリーニング作業を行って選定させるものであり、本発明と既存技術の組み合わせにより容易に達成可能である。For example, when blending and preparing the fluorine-containing curable composition of the present invention, in addition to the components (A) and (B) according to the present invention, when combining various formulations in the above-described fluorine-containing curable composition In addition, when emphasizing low refractive index characteristics and low reflection characteristics using this, reactive hollow silica, hollow silica having no reactive group, or trifunctional or higher non-fluorine-based component (C) In the case of using a polyfunctional acrylic compound and improving the film strength and scratch resistance, two or more non-fluorine-based polyfunctional acrylic compounds are blended in a suitable amount as the component (C), or hardness In order to balance flexibility, it is possible to perform a combination of a non-fluorinated hexafunctional or higher polyfunctional acrylic compound and a trifunctional or lower acrylic compound as the component (C). Known acrylic curable compositions It can be easily inferred from knowledge of compounding.
When obtaining an article by applying the fluorine-containing curable composition of the present invention, for example, when applying the composition to a film substrate, the coating thickness is adjusted to prevent interference fringes. By adjusting the thickness of the film base material to make it easier to suppress curling, and by adjusting the elastic modulus of the base film, deformation and coating after curing of the fluorine-containing curable composition can be prevented. Suppression of film cracking, etc., can be achieved easily by combining the present invention and existing technology by performing screening work based on a combination of existing conditions according to each characteristic.
以下に、合成例、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。 Synthesis examples, examples, and comparative examples are shown below to specifically describe the present invention, but the present invention is not limited to the following examples.
[合成例1]含フッ素アクリル化合物(A-1)の合成
還流装置と攪拌装置を備えた300L四つ口フラスコに、平均構造が下記式(I)
HOCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OH (I)
で表される化合物(但し、-CF2CF2O-と-CF2O-の繰り返し単位の配列はランダムである)100g(OH基 0.0508mol)、下記式(II)
CH2=CHC(=O)OCH2CH2-N=C=O (II)
で表される化合物7.17g、ヘキサフルオロメタキシレン200gを仕込み、乾燥空気雰囲気下で攪拌しながら40℃まで加熱した。ついで、0.01gのジオクチル錫ジラウレートを投入し、6時間加熱攪拌を継続してから、加熱を停止した。反応液の19F-NMRにより、-OCF2CH2OHのCF2に由来するピーク(-81.1ppm、-83.15ppm)がすべて、-OCF2CH2OC(=O)-に由来する(-78.4ppm、-80.4ppm)に変化したのを確認した。得られた反応液に活性炭2gを投入し、室温で3時間攪拌したのちに、ろ過板でろ過を行った。得られたろ液を50℃で減圧留去し、目的とするフッ素含有率57.5質量%の下記(A-1)の平均構造を有する化合物97.8gを得た。
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-1)[Synthesis Example 1] Synthesis of fluorine-containing acrylic compound (A-1) In a 300 L four-necked flask equipped with a reflux device and a stirring device,
HOCH2CF2O ( CF2CF2O )20.1 ( CF2O ) 21.6CF2CH2OH ( I )
100 g (OH group: 0.0508 mol) of a compound represented by the following formula (II) (wherein the arrangement of repeating units of -CF 2 CF 2 O- and -CF 2 O- is random)
CH2 =CHC(=O) OCH2CH2 - N=C=O (II)
7.17 g of the compound represented by and 200 g of hexafluorometaxylene were charged and heated to 40° C. while stirring in a dry air atmosphere. Then, 0.01 g of dioctyltin dilaurate was added, and heating and stirring were continued for 6 hours, after which the heating was stopped. According to 19 F-NMR of the reaction solution, the peaks (-81.1 ppm, -83.15 ppm) derived from CF 2 of -OCF 2 CH 2 OH are all derived from -OCF 2 CH 2 OC(=O)-. It was confirmed that it changed to (-78.4 ppm, -80.4 ppm). 2 g of activated carbon was added to the obtained reaction solution, and the mixture was stirred at room temperature for 3 hours, and then filtered with a filter plate. The obtained filtrate was distilled off under reduced pressure at 50° C. to obtain 97.8 g of the desired compound having the following average structure (A-1) with a fluorine content of 57.5 mass %.
CH2 =CHC( = O) OCH2CH2NHC ( = O ) OCH2CF2O ( CF2CF2O ) 20.1 ( CF2O ) 21.6CF2CH2OC (=O)NHCH2CH2OC (=O) CH=CH 2 (A-1)
[合成例2]含フッ素アクリル化合物(A-2)の合成
合成例1において、上記式(I)の代わりに、平均構造として下記式(III)
HOCH2CF2O(CF2CF2O)31.1(CF2O)30.5CF2CH2OH
(III)
で表される化合物(但し、-CF2CF2O-と-CF2O-の繰り返し単位の配列はランダムである)100g(OH基 0.0345mol)を用い、上記式(II)の化合物の配合量を4.86gに変更した以外は合成例1と同様の手順で操作を行い、平均構造として下記のフッ素含有率59.2質量%の化合物(A-2)96.2gが得られた。
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2O(CF2CF2O)31.1(CF2O)30.5CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-2)[Synthesis Example 2] Synthesis of fluorine-containing acrylic compound (A-2) In Synthesis Example 1, instead of the above formula (I), the following formula (III) as an average structure
HOCH2CF2O ( CF2CF2O ) 31.1 ( CF2O ) 30.5CF2CH2OH
(III)
Using 100 g (OH group: 0.0345 mol) of the compound represented by the above formula (II) (wherein the arrangement of the repeating units of —CF 2 CF 2 O— and —CF 2 O— is random), The same procedure as in Synthesis Example 1 was performed except that the amount was changed to 4.86 g, and 96.2 g of the following compound (A-2) having a fluorine content of 59.2% by mass as an average structure was obtained. .
CH2 = CHC(=O) OCH2CH2NHC (=O ) OCH2CF2O ( CF2CF2O ) 31.1 ( CF2O ) 30.5CF2CH2OC (= O ) NHCH2CH2OC (=O) CH=CH 2 (A-2)
[合成例3]含フッ素アクリル化合物(A-3)の合成
還流装置と攪拌装置を備えた300L四つ口フラスコに、式(I)の化合物100g(OH基 0.0508mol)、トリエチルアミン7.20g、ヘキサフルオロメタキシレン150g、室温下、乾燥空気雰囲気下で攪拌しながら、アクリル酸クロライド6.38g(0.0704mol)とヘキサフルオロメタキシレン50gの混合液を30分かけて滴下した。6時間攪拌を継続してから停止し、ろ紙によるろ過を行った。得られたろ液はヘキサン1,000g中に投入し、発生した沈殿物を回収し、ヘキサフルオロメタキシレン100gで溶解させてから50℃で溶剤の減圧留去を行い、19F-NMRで目的とする下記の平均構造を有するフッ素含有率60.0質量%の化合物(A-3)90.5gが得られたことを確認した。
CH2=CHC(=O)OCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OC(=O)CH=CH2 (A-3)[Synthesis Example 3] Synthesis of fluorine-containing acrylic compound (A-3) In a 300 L four-necked flask equipped with a reflux device and a stirrer, 100 g of the compound of formula (I) (OH group: 0.0508 mol) and 7.20 g of triethylamine were added. , 150 g of hexafluorometa-xylene was added dropwise over 30 minutes while stirring at room temperature in a dry air atmosphere. Stirring was continued for 6 hours and then stopped, followed by filtration with filter paper. The resulting filtrate was poured into 1,000 g of hexane, the generated precipitate was recovered, dissolved in 100 g of hexafluorometa-xylene, the solvent was distilled off under reduced pressure at 50° C., and the desired product was obtained by 19 F-NMR. It was confirmed that 90.5 g of compound (A-3) having a fluorine content of 60.0% by mass and having the following average structure was obtained.
CH2 =CHC(=O)OCH2CF2O(CF2CF2O)20.1 ( CF2O ) 21.6CF2CH2OC ( = O)CH= CH2 ( A - 3)
[合成例4]含フッ素アクリル化合物(A-4)の合成
合成例1において、上記式(I)の代わりに、平均構造として下記式(IV)
CF3O(CF2CF2O)20.1(CF2O)19.2CF2CH2OH (IV)
で表される化合物(但し、-CF2CF2O-と-CF2O-の繰り返し単位の配列はランダムである)100g(OH基 0.0264mol)を用い、上記式(II)の化合物の配合量を4.11gに変更し、ジオクチル錫ジラウレートの代わりに、オルトチタン酸テトラキス(2-エチルヘキシル)0.2gを用いた以外は合成例1と同様の手順で操作を行い、平均構造として下記のフッ素含有率60.2質量%の化合物(A-4)97.5gが得られた。
CF3O(CF2CF2O)20.1(CF2O)19.2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-4)[Synthesis Example 4] Synthesis of fluorine-containing acrylic compound (A-4) In Synthesis Example 1, instead of the above formula (I), the following formula (IV) as an average structure
CF3O ( CF2CF2O ) 20.1 ( CF2O ) 19.2CF2CH2OH ( IV )
Using 100 g (0.0264 mol of OH groups) of the compound represented by the above formula (II) (wherein the arrangement of repeating units of —CF 2 CF 2 O— and —CF 2 O— is random), The same procedure as in Synthesis Example 1 was repeated except that the amount was changed to 4.11 g and 0.2 g of tetrakis(2-ethylhexyl) orthotitanate was used instead of dioctyltin dilaurate. 97.5 g of compound (A-4) having a fluorine content of 60.2% by mass was obtained.
CF3O ( CF2CF2O ) 20.1 ( CF2O ) 19.2CF2CH2OC (=O) NHCH2CH2OC ( =O)CH= CH2 (A - 4 )
[合成例5]含フッ素アクリル化合物(B-1)の合成
乾燥窒素雰囲気下で、還流装置と攪拌装置を備えた5,000mL三つ口フラスコに、下記式
CH2=CH-CH2-O-CH2-Rf’-CH2-O-CH2-CH=CH2
Rf’:-CF2O(CF2CF2O)20.9(CF2O)21.2CF2-
で表されるパーフルオロポリエーテル1,000g(0.245mol)と、m-キシレンヘキサフロライド1,400g、及びテトラメチルシクロテトラシロキサン722g(3.00mol)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0.884g(Pt単体として2.2×10-6molを含有)を投入し、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、溶剤と過剰のテトラメチルシクロテトラシロキサンを減圧留去した。その後活性炭処理を行い、下記式で示される無色透明の液状化合物(V)993gを得た。
乾燥空気雰囲気下で、上記で得られた化合物(V)50.0g(Si-H基量0.0657mol)に対して、2-アリルオキシエタノール7.05g(0.0690mol)、m-キシレンヘキサフロライド50.0g、及び塩化白金酸/ビニルシロキサン錯体のトルエン溶液0.0442g(Pt単体として1.1×10-7molを含有)を混合し、100℃で4時間攪拌した。1H-NMR及びIRでSi-H基が消失したのを確認した後、溶剤と過剰の2-アリルオキシエタノールを減圧溜去し、活性炭処理を行い、下記式で示される淡黄色透明の液体含フッ素アルコール化合物(VI)54.9gを得た。
乾燥空気雰囲気下で、得られた含フッ素アルコール化合物(VI)50.0g(水酸基量0.058mol)に対して、THF50.0gとアクリロイルオキシエチルイソシアネート9.00g(0.0638mol)を混合し、50℃に加熱した。そこにオルトチタン酸テトラキス(2-エチルヘキシル)0.15gを添加し、50℃下24時間攪拌した。加熱終了後、80℃/0.266kPaで減圧留去を行い、淡黄色のペースト状物質58.5gを得た。1H-NMR及びIRの結果から下記に示す、フッ素含有率41.0質量%の含フッ素アクリル化合物であることを確認した。
Rf ': -CF2O ( CF2CF2O ) 20.9 ( CF2O ) 21.2CF2-
1,000 g (0.245 mol) of perfluoropolyether represented by , 1,400 g of m-xylene hexafluoride, and 722 g (3.00 mol) of tetramethylcyclotetrasiloxane were charged and heated to 90°C while stirring. heated. 0.884 g of a toluene solution of a platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 2.2×10 −6 mol as Pt alone) was added thereto, and the internal temperature was maintained at 90° C. or higher. Stirring was continued for 4 hours. After confirming the disappearance of the starting allyl group by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, the mixture was treated with activated carbon to obtain 993 g of a colorless and transparent liquid compound (V) represented by the following formula.
In a dry air atmosphere, 7.05 g (0.0690 mol) of 2-allyloxyethanol, m-xylene hexa 50.0 g of fluoride and 0.0442 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 1.1×10 −7 mol as Pt alone) were mixed and stirred at 100° C. for 4 hours. After confirming the disappearance of the Si—H group by 1 H—NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and the residue was treated with activated carbon to give a pale yellow transparent liquid represented by the following formula. 54.9 g of fluorine-containing alcohol compound (VI) was obtained.
In a dry air atmosphere, 50.0 g of the obtained fluorine-containing alcohol compound (VI) (0.058 mol of hydroxyl group) was mixed with 50.0 g of THF and 9.00 g (0.0638 mol) of acryloyloxyethyl isocyanate, Heated to 50°C. 0.15 g of tetrakis(2-ethylhexyl) orthotitanate was added thereto and stirred at 50° C. for 24 hours. After completion of heating, distillation under reduced pressure was carried out at 80° C./0.266 kPa to obtain 58.5 g of a pale yellow pasty substance. From the results of 1 H-NMR and IR, it was confirmed to be a fluorine-containing acrylic compound with a fluorine content of 41.0% by mass as shown below.
[合成例6]含フッ素アクリル化合物(B-2)の合成
乾燥窒素雰囲気下で、還流装置と攪拌装置を備えた500mL三つ口フラスコに、下記式
CH2=CH-CH2-O-CH2-Rf”-CH2-O-CH2-CH=CH2
Rf”:-CF2O(CF2CF2O)9.8(CF2O)9.1CF2-
で表されるパーフルオロポリエーテル100g(0.0501mol)と、m-キシレンヘキサフロライド100g、及びテトラメチルシクロテトラシロキサン121g(0.502mol)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1.1×10-6molを含有)を投入し、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、溶剤と過剰のテトラメチルシクロテトラシロキサンを減圧留去した。その後活性炭処理を行い、下記式で示される無色透明の液状化合物(VII)112gを得た。
乾燥空気雰囲気下で、上記で得られた化合物(VII)50.0g(Si-H基量0.121mol)に対して、2-アリルオキシエタノール15.1g(0.149mol)、m-キシレンヘキサフロライド100.0g、及び塩化白金酸/ビニルシロキサン錯体のトルエン溶液0.0884g(Pt単体として2.2×10-7molを含有)を混合し、100℃で4時間攪拌した。1H-NMR及びIRでSi-H基が消失したのを確認した後、溶剤と過剰の2-アリルオキシエタノールを減圧溜去し、活性炭処理を行い、下記式で示される淡黄色透明の液体含フッ素アルコール化合物(VIII)60.2gを得た。
乾燥空気雰囲気下で、得られた含フッ素アルコール化合物(VIII)50.0g(水酸基量0.097mol)に対して、THF50.0gとアクリロイルオキシエチルイソシアネート17.7g(0.125mol)を混合し、50℃に加熱した。そこにジオクチル錫ジラウレート0.05gを添加し、50℃下24時間攪拌した。加熱終了後、80℃/0.266kPaで減圧留去を行い、淡黄色の高粘調液体63.5gを得た。1H-NMR及びIRの結果から下記に示す、フッ素含有率29.7質量%の含フッ素アクリル化合物であることを確認した。
Rf": -CF 2 O (CF 2 CF 2 O) 9.8 (CF 2 O) 9.1 CF 2 -
100 g (0.0501 mol) of perfluoropolyether represented by , 100 g of m-xylene hexafluoride, and 121 g (0.502 mol) of tetramethylcyclotetrasiloxane were added and heated to 90°C while stirring. 0.442 g of a toluene solution of a platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 −6 mol as Pt alone) was added thereto, and the internal temperature was maintained at 90° C. or higher. Stirring was continued for 4 hours. After confirming the disappearance of the starting allyl group by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was performed to obtain 112 g of a colorless and transparent liquid compound (VII) represented by the following formula.
In a dry air atmosphere, 15.1 g (0.149 mol) of 2-allyloxyethanol, m-xylenehexa 100.0 g of fluoride and 0.0884 g of a toluene solution of a chloroplatinic acid/vinylsiloxane complex (containing 2.2×10 −7 mol of Pt alone) were mixed and stirred at 100° C. for 4 hours. After confirming the disappearance of the Si—H group by 1 H—NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and the residue was treated with activated carbon to give a pale yellow transparent liquid represented by the following formula. 60.2 g of fluorine-containing alcohol compound (VIII) was obtained.
In a dry air atmosphere, 50.0 g of THF and 17.7 g (0.125 mol) of acryloyloxyethyl isocyanate were mixed with 50.0 g of the obtained fluorine-containing alcohol compound (VIII) (0.097 mol of hydroxyl group), Heated to 50°C. 0.05 g of dioctyltin dilaurate was added thereto and stirred at 50° C. for 24 hours. After completion of heating, distillation under reduced pressure was carried out at 80° C./0.266 kPa to obtain 63.5 g of a pale yellow highly viscous liquid. From the results of 1 H-NMR and IR, it was confirmed to be a fluorine-containing acrylic compound with a fluorine content of 29.7 mass % shown below.
[実施例1~11、比較例1~7]
本発明の含フッ素硬化性組成物の原料成分を下記に示す。
(A)含フッ素アクリル化合物
(A-1)合成例1で得られた含フッ素アクリル化合物
(A-2)合成例2で得られた含フッ素アクリル化合物
(A-3)合成例3で得られた含フッ素アクリル化合物
(A-4)合成例4で得られた含フッ素アクリル化合物
(B)含フッ素アクリル化合物
(B-1)合成例5で得られた含フッ素アクリル化合物
(B-2)合成例6で得られた含フッ素アクリル化合物
(C)非フッ素化アクリル化合物
(C-1)ペンタエリスリトールエトキシテトラアクリレート
[ダイセルオルネクス社製 EBECRYL 40]
(C-2)ペンタエリスリトールトリアクリレート
(C-3)ペンタエリスリトールトリアクリレートとヘキサメチレンジイソシアネートの反応物からなる多官能アクリレート[共栄社化学社製 UA-306H]
(D)光重合開始剤
(D-1)1-ヒドロキシシクロヘキシルフェニルケトン(商品名:IRGACURE 184、BASFジャパン社製)
(D-2)2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチルプロピオニル)ベンジル]フェニル}-2-メチルプロパン-1-オン(商品名:IRGACURE 127、BASFジャパン社製)[Examples 1 to 11, Comparative Examples 1 to 7]
Raw material components of the fluorine-containing curable composition of the present invention are shown below.
(A) Fluorine-containing acrylic compound (A-1) Fluorine-containing acrylic compound obtained in Synthesis Example 1 (A-2) Fluorine-containing acrylic compound obtained in Synthesis Example 2 (A-3) Obtained in Synthesis Example 3 Fluorine-containing acrylic compound (A-4) Fluorine-containing acrylic compound obtained in Synthesis Example 4 (B) Fluorine-containing acrylic compound (B-1) Fluorine-containing acrylic compound obtained in Synthesis Example 5 (B-2) Synthesis Fluorine-containing acrylic compound obtained in Example 6 (C) Non-fluorinated acrylic compound (C-1) Pentaerythritol ethoxy tetraacrylate [EBECRYL 40 manufactured by Daicel Ornex Co., Ltd.]
(C-2) Pentaerythritol triacrylate (C-3) Polyfunctional acrylate composed of a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate [UA-306H manufactured by Kyoeisha Chemical Co., Ltd.]
(D) Photopolymerization initiator (D-1) 1-hydroxycyclohexylphenyl ketone (trade name: IRGACURE 184, manufactured by BASF Japan)
(D-2) 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: IRGACURE 127, BASF Japan) made)
[含フッ素硬化性組成物の調製]
成分(A)及び(B)は全てメチルエチルケトンで20質量%に、成分(C)は酢酸ブチルで40質量%に希釈を行った。また(C-1)の希釈溶剤を酢酸ブチルから2-プロパノールに替えて40質量%に希釈したものを(C-4)として配合した。
成分(A)~(D)の各成分の溶剤成分を除いた配合比として下記表1となるように混合し、含フッ素硬化性組成物を得た。[Preparation of fluorine-containing curable composition]
All components (A) and (B) were diluted with methyl ethyl ketone to 20% by mass, and component (C) was diluted with butyl acetate to 40% by mass. In addition, 2-propanol was used instead of butyl acetate as the diluting solvent of (C-1) and diluted to 40% by mass was blended as (C-4).
Components (A) to (D) were mixed so as to have the compounding ratio shown in Table 1 below, excluding the solvent component, to obtain a fluorine-containing curable composition.
[組成物の溶解状態]
各組成物の溶解状態(塗工液外観)を目視で観察した。なお、沈殿物が発生した組成物についてはこれ以降の評価を行わなかった。結果を表2に示す。[Dissolution state of composition]
The dissolution state (appearance of coating liquid) of each composition was visually observed. Further evaluation was not performed for the composition in which a precipitate was generated. Table 2 shows the results.
塗工と硬化物の作製
実施例及び比較例の各組成物をポリカーボネート基板上にワイヤーバーNo.7で塗工した(ウエット膜厚16.0μm)。塗工後100℃、1分間の乾燥を行った後、コンベヤ式メタルハライドUV照射装置(パナソニック電工製)を使用し、窒素雰囲気中で、積算照射量400mJ/cm2の紫外線を塗工面に照射して組成物を硬化させ、厚み5μmの硬化膜を得た。 Coating and preparation of cured product Each composition of Examples and Comparative Examples was coated on a polycarbonate substrate with a wire bar No. 1. 7 (wet film thickness: 16.0 µm). After drying at 100°C for 1 minute after coating, the coated surface was irradiated with UV rays with an accumulated irradiation dose of 400 mJ/cm 2 in a nitrogen atmosphere using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works). The composition was cured with a mortar to obtain a cured film having a thickness of 5 μm.
[撥水撥油性の評価]
1)水接触角測定
接触角計(協和界面科学社製 DropMaster)を用い、水2μLの液滴を硬化膜上に滴下して1秒後の水接触角を測定した。N=5の平均値を測定値とした。結果を表2に示す。
2)オレイン酸接触角測定
接触角計(協和界面科学社製 DropMaster)を用い、オレイン酸4μLの液滴を硬化膜上に滴下して1秒後のオレイン酸接触角を測定した。N=5の平均値を測定値とした。結果を表2に示す。[Evaluation of water and oil repellency]
1) Measurement of Water Contact Angle Using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.), a water droplet of 2 μL was dropped on the cured film, and the water contact angle was measured one second later. The average value of N=5 was used as the measured value. Table 2 shows the results.
2) Oleic acid contact angle measurement Using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.), a droplet of 4 μL of oleic acid was dropped on the cured film, and the oleic acid contact angle was measured one second after. The average value of N=5 was used as the measured value. Table 2 shows the results.
[動摩擦係数の測定]
ベンコット(旭化成社製)に対する硬化膜の動摩擦係数を、表面性試験機14FW(新東科学社製)を用いて下記条件で測定した。結果を表2に示す。
接触面積:10mm×35mm
荷重:100g[Measurement of dynamic friction coefficient]
The dynamic friction coefficient of the cured film against BEMCOT (manufactured by Asahi Kasei Corp.) was measured under the following conditions using a surface property tester 14FW (manufactured by Shinto Kagaku Corp.). Table 2 shows the results.
Contact area: 10mm x 35mm
Load: 100g
[マジックハジキ性の評価]
硬化膜表面にマジックペン(ゼブラ社製 ハイマッキー太字)で直線を描き、そのハジキ具合を目視観察によって評価した。結果を表2に示す。[Evaluation of magic repellency]
A straight line was drawn on the surface of the cured film with a magic pen (Himakkie bold type, manufactured by Zebra), and the degree of repelling was evaluated by visual observation. Table 2 shows the results.
[マジック拭き取り性の評価]
硬化膜表面にマジックペン(ゼブラ社製 ハイマッキー太字)で直線を描き、1分後にティッシュペーパーで軽く3回擦って、マジックの跡が残らなかったものを「拭き取れる」、跡が残ったものを「拭き取れない」で評価した。結果を表2に示す。[Evaluation of magic wiping performance]
Draw a straight line on the surface of the cured film with a magic pen (Himackey Bold by Zebra), and after 1 minute, lightly rub it 3 times with a tissue paper. was evaluated as "cannot be wiped off". Table 2 shows the results.
上記の結果から明らかなように、成分(B)を配合せず、成分(A)、(C)のみを配合した比較例1~3の組成物は、組成物の溶解状態が悪く沈殿物が発生するが、成分(A)、(B)、(C)を配合した本発明の実施例1~11の組成物は、透明均一な塗工液を作製することができ、また、本発明の実施例1~11の組成物は、成分(A)を配合せず、成分(B)、(C)のみを配合した比較例4、5、7の組成物に比べて、高い撥液性と滑り性を持つ表面を形成することができる。 As is clear from the above results, the compositions of Comparative Examples 1 to 3, in which only the components (A) and (C) were blended without blending the component (B), had a poor dissolution state of the composition and formed precipitates. However, the compositions of Examples 1 to 11 of the present invention, in which components (A), (B), and (C) are blended, can prepare a transparent and uniform coating liquid, and the The compositions of Examples 1 to 11 did not contain the component (A) and had higher liquid repellency than the compositions of Comparative Examples 4, 5 and 7 containing only the components (B) and (C). A slippery surface can be formed.
Claims (11)
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(式中、Rf1はフッ素原子、又は酸素原子を含んでいてもよい炭素数1~8の1価の含フッ素アルキル基であり、Rf2は下記の2種類の繰り返し単位
-CF2O-
-CF2CF2O-
がランダムに配列した分子量600~20,000の2価のパーフルオロポリエーテル基である。Z1は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも1種のヘテロ原子を含んでいてもよい炭素数1~20の2価の炭化水素基、-C(=O)-及び-C(=O)O-から選ばれる連結基であり、該2価の炭化水素基は途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。X1は独立に酸素原子及び/又は窒素原子を含んでいてもよい(メタ)アクリル基を有する1価の有機基であり、X2は水酸基又はX1である。)
で表される成分(A)、
フルオロポリエーテルを主鎖に持つ直鎖ポリマーの1分子中のそれぞれの分子鎖末端にそれぞれ2個以上の(メタ)アクリル基を有し、1分子中に平均して4~10個の(メタ)アクリル基を有し、フッ素含有率が25質量%以上45質量%未満の化合物からなる、下記一般式(3)
で表される成分(B)、及び
フルオロポリエーテル構造を含まず、1分子中に平均して2個以上の(メタ)アクリル基を有する非フッ素化アクリル化合物からなる成分(C)を必須成分とし、成分(C)100質量部に対して、成分(A)と成分(B)の配合量の合計が0.1~10質量部であり、かつ成分(B)100質量部に対する成分(A)の配合量が3~50質量部である含フッ素硬化性組成物。 A linear polymer having a fluoropolyether as the main chain, having one or two (meth)acrylic groups at one or both ends of the molecular chain, and the (meth)acrylic group contained in one molecule The following general formula (1) or (2) consisting of a compound having an average number of 2 or less and a fluorine content of 48% by mass or more and less than 62% by mass
Rf 1 -O-Rf 2 -CF 2 -Z 1 -X 1 (1)
X 2 -Z 1 -CF 2 O-Rf 2 -CF 2 -Z 1 -X 1 (2)
(In the formula, Rf 1 is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms which may contain an oxygen atom, and Rf 2 is one of the following two types of repeating units —CF 2 O—
-CF2CF2O- _
is a randomly arranged divalent perfluoropolyether group with a molecular weight of 600 to 20,000. Z 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom, -C(=O)- and - A linking group selected from C(=O)O—, the divalent hydrocarbon group may contain a cyclic structure in the middle, and some of the hydrogen atoms bonded to the carbon atoms are substituted with fluorine atoms. may X 1 is independently a monovalent organic group having a (meth)acryl group optionally containing an oxygen atom and/or a nitrogen atom, and X 2 is a hydroxyl group or X 1 . )
Component (A) represented by
Each molecule of a linear polymer having a fluoropolyether as a main chain has two or more (meth)acrylic groups at each molecular chain end, and an average of 4 to 10 (meth)acrylic groups per molecule. ) The following general formula (3), which has an acrylic group and is composed of a compound having a fluorine content of 25% by mass or more and less than 45% by mass
A component (B) represented by and a component (C) consisting of a non-fluorinated acrylic compound that does not contain a fluoropolyether structure and has an average of two or more (meth)acrylic groups in one molecule (C) as an essential component and the total amount of component (A) and component (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of component (C), and component (A ) in an amount of 3 to 50 parts by mass.
-C(=O)-
-C(=O)O-
-C(=O)OCH2-
-C(=O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(=O)NH-
-CH2OC(=O)NHCH2CH2- 4. The fluorine-containing curable composition according to any one of claims 1 to 3, wherein in component (A), Z 1 in general formula (1) or (2) has any of the following structures.
-C(=O)-
-C(=O)O-
-C(=O) OCH2-
-C ( =O) OCH2CH2-
-CH2-
-CH 2 O-
-CH2OCH2- _
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OC (=O)NH-
-CH2OC ( =O) NHCH2CH2-
-OC(=O)CH=CH2
-OC(=O)C(CH3)=CH 2
-CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
-C(CH3)[CH2OC(=O)CH=CH2] 2
-C(CH2CH3)[CH2OC(=O)CH=CH2]2
-C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2 5. The fluorine-containing curable composition according to any one of claims 1 to 4, wherein in component (A), X 1 in general formula (1) or (2) is represented by any one of the following: .
-OC(=O)CH= CH2
-OC(=O)C( CH3 )= CH2
- CH[ CH2OC (=O)CH= CH2 ][ CH2OC (=O)C( CH3 )= CH2 ]
-C( CH3 )[ CH2OC (=O)CH= CH2 ] 2
- C( CH2CH3 )[ CH2OC (=O)CH = CH2 ] 2
-C( CH2CH3 )[ CH2OC ( = O)C( CH3 )= CH2 ] 2
Rf1ORf2CF2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2
Rf1ORf2CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
Rf1ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2
HOCH2CF2ORf2CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2
CH2=C(CH3)C(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CF2ORf2CF2CH2OC(=O)CH=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)CH=CH2
CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OCH2OC(=O)C(CH3)=CH2
CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2
(式中、Rf1、Rf2は上記と同じである。) 6. The fluorine-containing acrylic compound according to any one of claims 1 to 5, wherein in component (A), the fluorine-containing acrylic compound represented by general formula (1) or (2) is represented by any one of the following: Curable composition.
Rf1ORf2CF2CH2OC (= O ) CH = CH2
Rf1ORf2CF2CH2OC (= O ) C ( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O )CH = CH2
HOCH2CF2ORf2CF2CH2OC ( = O )C ( CH3 ) = CH2
Rf1ORf2CF2C (=O) OCH2CH2OC (= O ) CH = CH2
Rf1ORf2CF2C ( = O) OCH2CH2OC (= O )C( CH3 )= CH2
HOCH2CF2ORf2CF2C ( = O) OCH2CH2OC (= O )CH = CH2
HOCH2CF2ORf2CF2C ( = O) OCH2CH2OC ( = O )C( CH3 ) = CH2
Rf1ORf2CF2C (=O)OCH[ CH2OC (=O)CH= CH2 ][ CH2OC (= O ) C ( CH3 )= CH2 ]
Rf1ORf2CF2CH2OC ( = O) NHCH2CH2OC ( = O )CH = CH2
Rf1ORf2CF2CH2OC (=O) NHCH2CH2OC ( = O )C( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O) NHCH2CH2OC (= O ) CH = CH2
HOCH2CF2ORf2CF2CH2OC (=O) NHCH2CH2OC ( = O ) C ( CH3 ) = CH2
HOCH2CF2ORf2CF2CH2OC ( = O)NHC ( CH3 )[ CH2OC ( = O )CH= CH2 ] 2
CH2 =C( CH3 ) C ( =O)OCH2CF2ORf2CF2CH2OC(= O )C( CH3 ) = CH2
CH2 = CHC (= O ) OCH2CF2ORf2CF2CH2OC (=O)C( CH3 ) = CH2
CH2 = CHC ( =O) OCH2CF2ORf2CF2CH2OC (=O)CH = CH2
CH2 = CHC ( = O ) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OCH2OC( = O ) CH = CH2
CH2 =C ( CH3 ) C ( = O ) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OCH2OC(= O )C( CH3 ) = CH2
CH2 = CHC (=O) OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OC( = O ) NHCH2CH2OC ( = O ) CH = CH2
(In the formula, Rf 1 and Rf 2 are the same as above.)
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2- 7. The fluorine-containing curable composition according to any one of claims 1 to 6, wherein in component (B), Z 3 in general formula (3) is represented by any one of the following formulae.
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _
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